Can 首 be used to refer to students who have just graduated and not yet found a job? The example sentences in WWWJDIC all use the word "" in the "fire" sense (e.g. ) hence I was wondering is the term only used to refer to "firing" someone? Or is it also used to refer to students who have just graduated and not yet found a job (they have never had a job before so they can't be fired can they)?

No, you can't use to refer to students who have just graduated and don't have a job yet.

Pardon me if I am incorrect here, but I think maybe you think that "" means "turn (someone) into a ", and so is an idiom for "unemployed person" or something. [Edit: My apologies, it looks like you were just taking the word of EDICT, which (wrongly, I think) makes exactly this claim.] This is not the case, though. "" ultimately comes from the metaphor of beheading (!) and although it can be extended to other forms ( etc.), it only refers to the act of firing/being fired, not to the result (being unemployed). So, it is not relevant to recent graduates... or any unemployed person, actually, except insofar as you can talk about their past: "She was fired in May," etc.)