If you were in an ESOP (Employee Stock Option Plan) and actually purchased your options while you were employed, you can sell your shares without penalty. If you did not exercise the option while you were employed, it is unlikely you have any shares.
ESOPs are not usually "enrollment based". You do not have to "sign up" or contribute money to be in the ESOP.
What you PROBABLY meant was that you were enrolled in an ESPP (Employee Stock Purchase Plan). If this was the case, there would have been regular withdrawals from your paycheck to buy company stock at a discount. If you did that, then your shares (if you have not already sold them) - - are with the brokerage that your company plan uses.
It depends on how the ESOP is structured. Is the ESOP an option in the line up of investment options within the 401k plan? Is so, the withdrawal of money after you sell the stock must follow the income tax and penalty regulations, 10% percent excise tax (which is not deductable), and ordinary income tax marginal rate brackets (capital gains tax rates do not apply). See IRS Publication 590.
If the set up of the ESOP is outside the 401k plan, capital gains taxes may be used depending on the holding period for the stock. Otherwise the ordinary income tax marginal rate brackets will apply.
The timing may be dependent on whether the shares of the company used in the ESOP are publicly available on the stock exchanges. If so the settlement period for a sale and to get your money should be around 3 days. The administrator may take some minimal time for them to process the paperwork.
are there penalties like 401k?
You bet there is. 10% early withdrawal penalty & 20 - 30% taxes (federal & state).
I have been enrolled in a 401k and a ESOP while employed but now I have left and need the money. I have heard a couple different things. One thing I heard is that you have to wait a year to even receive the money. However, someone told me they had access to it right after they left. If you are able to get it imminently, are there penalties like 401k?