The face value of any bill or coin simply refers to its denomination, so the face value of any $1 bill is one dollar (and the face value of a quarter is 25¢, of a penny is 1¢, and so on.)
The collector or market value of a bill or coin is what it's actually worth to a collector on the open market. For that information, please see the Related Question.
In the case of a rare item the market value is almost always higher than the face value. Common items - e.g. a circulated 2010 dime - have no extra market value so their face value is the same as their value to a collector. And in some cases, for example obsolete currency that's not in high demand, the face value can be more than the collector value.
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