Go to settings in the PES folder on your C drive and change controller layout instead of keyboard.
Anyway, I have been using the keyboard this is my setup.... my hand has carpal tunnel syndrome from it. I'm getting a USB/PSX converter today. Can't take this shit anymore. Online game suffers, even though I win almost every match (btw anyone wanna play me my game id is pa7-ka22-ro80, also shows up as ka-pa-ro - i'm on PC).
w a s d = up, right, down, left
LB = left shift
LT = left ctrl
RB = NUM_KEY 6
RT = NUM_KEY 9
X = NUM_KEY 1
A = NUM_KEY 2
B = NUM_KEY 3
Y = NUM_KEY 5