Birth Control ?

I got a birth control prescription today from my doctor as the hubby and I have decided to take some more time to TTC. But she said to start the pill on my first day of period. Hubby is away for 14 days and I'll be starting my period around that time...I want to DTD with hubs if I can so my question is...can I start taking the pill tomorrow so that it will be effective for when hubby,returns??