Gear may be equipped to units to increase their stats. Different pieces of gear can improve different stats, there are multiple possible combinations you can explore.
Each piece of gear will improve one main stat, and it may also improve other secondary stats as you level it up. This will depend on the Gear rarity.
Gear is unlocked once the player reaches the 15th battle in the Dark Map in Adventure Mode (battle 2-10 in the Zombie Village).