PES 2014 is designed to be controlled with current generation controllers and, while you may be able to play with older controllers, we do not officially support the use of them and cannot provide detailed troubleshooting if your run into problems.
If you are running into trouble when using the most up to date official controllers for PS3® (Sixaxis® and Sixaxis® DUALSHOCK®3), you will find helpful information here.
Enjoy PES 2014 with all its new features and advanced controls!