I work full time from 9-5 Monday through Friday. My son and my girlfriend both live at home with me. At the time being she is unemployed. I wanted to know even though she isn't working can I still apply for care4kids using my information so that she can start working? Or would I have to write down that I am my son's guardian and that his mother and I aren't together anymore.

Can I assume care4kids is some state funded program of some sort ?

Please be specific what county you live in, what state if in the US.

If she is ready to go start applying for jobs you could always tell them you need the care so she is able to go apply places and see what they say.
With you working and not her, unless you make a good bit of money, you would probably be eligible financially either way.