You could do this with PWM, but realize that you are going to need a ton of low pass filtering to get down to the same accuracy level as a true D/A. For example, suppose you use 1 usec. increments on the duty cycle. To divide a 5 volt signal into 0.01v steps, you will need a period of 500 usec. To reduce the PWM ripple to only 0.01v with a 1-pole RC filter, you will need a time constant of 500 periods, or 1/4 second. Maybe for your application you don't mind waiting a few seconds for a voltage change. But that is the kind of slow-moving performance you will have to put up with.