The excited-state dynamics and third-order nonlinear optical properties of a novel porphyrin side-chain polymer, 5-hydroxy-10,15,20-triphenyl-porphyrin-poly(glycidyl methacrylate) (HTPP-PGMA) have been comparatively studied with a monomelic compound, 5, 10, 15, 20-tetraphenylpoipliyrin (TPP) by using picosecond and femtosecond transient absorption and fluorescence spectroscopy techniques. The ultrafast initial fluorescence decay (-300 ps) and has been observed ?л HTPP-PGMA, which is absence in TPP. Picosecond transient mirrorless optical bistable responses have been observed in both HTPP-PGMA and TPP. The HTPP-PGMA exhibits a faster decay of the output pulses. The ultrafast excited-state dynamics observed in HTPP-PGMA can be explained by the charge transfer (CT) between the porphyrin chromophores.