Smirk
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A smirk refers to a smile evoking insolence, scorn, or offensive smugness. "A constant smirk upon the face, and a whifling activity of the body, are strong indications of futility," the Earl of Chesterfield once wrote in a letter to his son.[1] A smirk also refers to a fine piece of dust when it enters the eye. This often leads to an uncomfortable feeling, and results in the sufferer searching in their eye to remove the foreign item. This can cause the sufferer to pull a face similar to that of a smirk, hence the name[citation needed]. A common expression associated with the word smirk can be, "Get the smirk off your face!."
If someone is smirkative, it means they enjoy smirking very frequently. A smirkative person often has a smirk on his or her face.
A smirkative person usually smirks in a more pleasant sort of way than one would assume from the above definition of the term.
Another synonym that also means smirk is to fleer, when someone smirks frequently.
References
http://www.youtube.com/watch?v=3L2513JFJsY&feature=related#t=5m09s