I am currently unemployed. I have a 401k with my last company that did not match my contributions. It's not a lot of money and I would like to withdraw / put it towards my sisters business she plans to expand and to work. Interested in the penalties involved / the best way to go about this. Is that a type of investment to avoid some of the penalties?

You will pay taxes (state and federal) at your current tax rate plus a 10% Early Withdrawal Penalty.

The total tax load can eat up to 50% of the distribution, so it is probably NOT a good idea.