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Yes there is currently a 1% unavoidable chance to miss. Blizzard implemented a few of these failsafes in the game, to keep it interesting.
This only applies to casters. Melee will never miss when hit capped. Look at any parses from high end raiding rogues, if they are hit capped(363 for them) they will have 0 misses in the parse. That doesn't mean they hit every time, unless they are also expertise capped and attacking from behind(6.5% expertise i think, too lazy to look it up on EJs atm). Hit capped + exp capped + attacking from behind = never missing.
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Its kind of the same reason why you can't stack so much avoidance that you are never hit(damn near tho).
While this is true for most classes, rogues can actually stack enough pure avoidance(dodge+parry) to never be hit. Requires a couple of specific buffs, but it has been done.
To address the OP:
You are currently hit capped for raid bosses with precision. You are hit capped for everything else without precision. However, when soloing you will almost always be attacking an enemy from the front and all mobs can dodge and most can parry as well(casters can't dodge or parry while casting). So unless you are expertise capped you will see a fair amount of dodges/parries when soloing. The + exp trinket from heroic mgt is great for reducing the number of dodges/parries you will see(2.5% reduction when attacking from behind-just dodges/5% reduction when attacking from the front - 2.5% dodge + 2.5% parry).
Edited, Sep 2nd 2008 2:51pm by mahlerite