This is an interesting question. The simple answer is that we are really told explicitly whether or not physical pain was possible. We do know, however, that in the judgment of Eve, pain is mentioned:
To the woman he said, “I will surely multiply your pain in
childbearing; in pain you shall bring forth children. Your desire
shall be for your husband, and he shall rule over you.” Genesis 3:16 ESV
The phrase, "I will surely multiply your pain", could certainly indicate that physical pain was a possibility.
This brings up some theological questions though. It seems that death only exists as a penalty for sin, and it would seem that pain is related to death. Pain tells us that something is wrong physically (much like shame lets us know that something is wrong spiritually). Yet, the body seems to have been created for immortal life, so pain that indicates the destruction of the body in some way does not seem to fit.
So, if pain originated at the fall, the wording in Genesis 3:16 could indicate that pain would also be a part of something that was intended to be good rather than just with all things that are to our own destruction.
Yet, again, we are not explicitly told the answer to this question, so it seems the best we can do is contemplate what we do know.