When Dodging, the Amazon will lean back in the opposite direction of the attacker.
Dodge will work while attacking.
You probably don't want to put more than one point into Dodge. The benefit of additional points drops off significantly and you will end up with a fair bit of +skill gear. Meaning you will get the benefit without wasting points.
To anyone familiar with their natural agility, it should came as no surprise that the training regimen of an Amazon warrior includes exercises specifically designed to avoid potentially devastating blows in combat.
↑Diablo II Manual, page 57. Blizzard Entertainment, 2000.