In Diablo 2, critical hits are slightly different. Only (to my knowledge) the Barbarian and the Amazon have the ability to get critical hits without the use of items. Crits do 2x damage. When last I checked, the Barbarian's chance of a crit was his weapon mastery level times 2 over a hundred. Thus, if you have a maxed spear mastery and hit with your pike, you stand a 40% chance of doing double damage. Wow. That's a leeeeeeetle unbalanced, so I think they're turning it down in the expansion.
For the Amazon, the skill Critical Strike determines your chance of doing double damage. Especially useful with Multi-Shot and Jab.

A few uniques and, in the Expansion pack, which I've yet to buy, runes, will give your weapon (or boots, rings, crowns, pet hamsters, etc...) Deadly Strike. This is the same as a %chance to crit from weapon mastery or the skill Critical strike, however, AFAIK, it stacks differently. if you had a 21% crit from skills and a 25% crit from your weapon, they are both calculated differently and you stand a 5.25% chance of double critting, or doing quadruple damage. Multiple bonuses to Deadly Strike on weapons just improve the Deadly Strike percentage, they do not add a chance for 8x, 16x, etc... damage.

UPDATE: The Barbarian's weapon mastery level will now display the %chance of a crit, however it is lower since version 1.08.