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Hello, my name is Duotem and I'm a semi competitive player on PC(ign:Duotem). I've played on two different challenger teams and made it to wildcards in the AVGL Fall 2016 tournament. This guide assumes you know the jungle role and deals with the theory around the build.
Start
Bumba's Mask: Allows you to last hit jungle monsters for sustain and gold.
Death's Toll: Since Arachne is very basic attack focused for clear this provides a lot of sustain.
Potions: I prefer 2 health and 2 mana potions for sustain.
Build
Warrior Tabi: Your main source of damage early is going to be venomous bite so the power allows you to make that even better.
Heartseeker: A fairly cheap early item that provides movement speed and a venomous bite with all the heartseeker stacks will shred your opponent.
Shield of Regrowth: 300HP and 20% Cooldown Reduction allows you to fight longer and have increased uptime on venomous bite. The bite also triggers the passive ensuring almost no one will be able to run away from you.
Qin's Sais: This item hugely increases your damage through basic attacks and the passive accelerates the hp loss which makes your passive hit harder.
Stone Cutting Sword: Even more movement speed, a large amount of power, and protection steal. A solid all around item for this character.
The Executioner: This item really rounds out the build as up til now the only pen you really have is on stone cutting sword. It also provides a ton of attack speed which helps you shred through people late game.
Situational Defense Items
These items can be built in place of the Stone Cutting Sword
Winged Blade: A cheap item with solid stats. This is never a bad option and if the enemy team has a lot of slows.
Magi's Blessing: This item is very useful when diving the backline versus high crowd control comps.
Spirit Robe: If the enemy team really only has one form of cc setting up their damage this item may be better than magi's. It also provides a lot of protections and crowd control.
Relics
Purification Beads: A core relic should be built in every game. Prevents you from being cc'd and lets you stick on targets.
Blink Rune: My preferred aggressive relic. Arachne's main problem is mobility to engage on enemies. This allows you to just appear in the backline throw down spiders and murder a squishy without anyone noticing.
Sundering Spear: If the enemy team has a ton of problematic tanks then this may be preferable over Blink.
Aegis Amulet: If you find the enemy mage to be a huge problem then you can get aegis, but in most situations the aggressive relics will be better.
Predator: This is your passive. It increases the power of your basic attacks the lower the hp of your enemy gets.
Venomous Bite: The most important ability on Arachne. This ability deals a ton of damage while healing you for a large amount. Making sure to use this as soon as it comes up in fights will basically ensure you win the 1v1.
Max this first
Cocoon: Provides an attack speed steroid while also stunning your opponent if you hit them with the first 3 autos.
Max this last
Web: Shoots a web forward a set amount that is stopped by walls as well as enemy minions and gods. When broken two spiders are spawned that will attack and the enemy is revealed to Arachne. If the enemy is a god then they will be slowed and a trail of web that increases your movement speed will trail behind them.
Max this second as the slow duration increases with rank
Night Crawler: Arachne gets on her web and can't be damaged by most things. You want to use this mainly as an escape.
Level this whenever you can as the cooldown gets reduced with each level
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For example, I'd look to sell one starter when I had enough gold to finish stone cutting sword in this build.
For builds with only 1 starter its generally ok to sell the starter to complete the 5th item. For example, selling the starter to finish Rod of Tahuti 5th item on a mage because its a big power spike
In jungle you want the speed buff so you can rotate faster around the map to assist all the lanes and clear camps. The adc generally wants red, but can take purple if the support is far away. The support generally wants purple because he's the one in the middle of the enemy team. solo wants blue so they can stay in lane and farm longer to get ahead
Most common time to sell a starter is usually toward the end of a build. You absolutely sell it when all the rest of the slots are taken up and you need to get your last item, but you can also consider selling earlier, circumstances allowing.
For example, say with Duo's standard build here, you've got 2 starters...Bumba's and Death's. Death's is pretty much solely for sustain, while Bumba's has that function, but also provides some extra gold. If you're working on what would be the 5th item slot, Shield of Regrowth (2 starters plus 3 core), you backed, and you were short ~500 gold to finish Shield, you might consider selling Death's at that point...a full item later in the build is going to be more functional than DT. Yes, you lose out on the sustain, but Arachne already has it in her Venomous Bite, so she'll be just fine. Keep Bumba's because 1) it costs less and wouldn't sell for as much, and 2) it provides extra gold.
Does this help?