Yes, but only if you live in a country (or state) where online poker is licensed and regulated. According to PokerStars it allows one PayPal account per customer and allows for both deposits and withdrawals via PayPal. See PokerStars' real-money information page and cashier page to see if Paypal is an option for you.

PayPal is a trusted e-wallet accepted by many online poker providers. Whether you're scrolling through poker rooms or looking for a new place to play online poker for real money, you want to know that your money is safe. PayPal is a trusted e-wallet accepted by many online poker providers.