Peroxide-induced crosslinking of isotactic (iPP) and syndiotactic (sPP) polypropylene was investigated experimentally. It was found that the two polymers showed similar crosslinking behavior, with iPP having a higher crosslinking efficiency. Our electron spin resonance measurements elucidated that the attack of peroxide radicals on iPP and sPP chains took place at the same position, giving rise to similar spectral hyperfine structures. However, a lower radical concentration was observed in sPP than in iPP with the same peroxide concentration and temperature. This might be caused by steric hindrance to the hydrogen abstraction of peroxide radicals. This low concentration of radicals is believed to be responsible for the lower crosslinking efficiency found with the sPP system. The crosslinking of both polymers was determined by temperature and peroxide type and concentration. The crosslinking kinetics showed that the initial gelation rate increased Linearly with the peroxide concentration and temperature. It was also observed that, at high peroxide concentration levels, significant beta-scission and other side reactions occurred simultaneously, introducing carbonyl and unsaturated groups to the structure of the polymeric networks.