Err yeah sure that will work. My advice: read the four hour work week. Not for the four hours but for putting you in a position to work for yourself and work as an employee.
Focus obsessively on your productivity on your current job and take on no new tasks. Hopefully get your tasks done in 10 hours per week (very easy if you get rid of all possible meetings and phone calls). Use the extra time to work on your own startup.
If the extra time belongs to your employer, then so does the copyright on any work you do during that extra time. Don't write any programs, documentation or marketing literature on employer time. Do focus on productivity, though. You need to be in the habit of being productive.
It's probably wise to consult a lawyer about this, but for my part, I say go ahead and work on your employer's time. Understand that you are taking a calculated risk. If the risk (e.g. getting fired, losing ownership of your work) isn't worth it, don't do it. But if it is, then stay as productive as you were before at work while trying to be as efficient as possible (e.g. by using methods in the Four Hour Work Week) to squeeze out extra time for your project. On your own time, work as hard as you can without skimping on your other obligations (e.g. family, bills, etc.).
I believe California has a specific law that whatever you do for yourself is your own property, in regards to IP. I assume other states have similar laws on the books, but it isn't universal.
During those work hours, you can do stuff like pay bills and make phone calls that would normally occupy your off hours. Optimize your off hours, at expense of your work hours.
Focus obsessively on your productivity on your current job and take on no new tasks. Hopefully get your tasks done in 10 hours per week (very easy if you get rid of all possible meetings and phone calls). Use the extra time to work on your own startup.