X-ray photoelectron spectroscopy and Raman spectroscopy were used to determine the chemical change ofpolyphenylsilsesquioxane (PPSQ) during pyrolysis in flowing nitrogen. Two temperature ranges were found for pyrolysedPPSQ below and above 600℃, respectively. The former is related to the rearrangement of PPSQ backbone and the latterreflects that most of backbone structure of PPSQ might be broken down and unorganized. Carbon formed in carbonization ofPPSQ sample pyrolysed at 900℃ should be sp3 bonded carbon with crystallite size effects or defects.