PES 2014 is designed to be controlled with current generation controllers and we do not officially support the use of older controllers. You can find more information on the compatibility of older controllers here.
If you are experiencing trouble in PES 2014 with recent official controllers (Sixaxis® and Sixaxis® DUALSHOCK®3) you might want to make sure that no older controllers or non-official PS3® controllers are connected to your PS3® as those can influence the performance of other controllers.
You will find further troubleshooting at the support page of PS3® with helpful instructions to set up your controller best for playing:
PS3® customer support