Yes, it is possible.
If you initiate the domain transfer on the day of expiration, you can complete the .com domain transfer on the same day itself, provided you login to the source account, from which you are transfering the account and confirm the transfer. If you do not confirm, in general after the time out period of 5 days, the domain will automatically be accepted and transferred.
Domain transfer during grace period
Domain transfer is possible during grace period also, however, your souce domain registran can levy nominal charges on you. If the domain is not yet expired, you do not need to pay a single penny.