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Resonance Raman spectra (RRs) of tetra(4-aminophenyl) porphine (TAPP) were obtained, and density functional calculations were done to help the elucidation of the photorelaxation dynamics of Soret (Bxand Byband) and Qyelectronic transitions. The RRs indicate that the photorelaxation dynamics for the S0→ S3excited electronic state is predominantly along the totally symmetric porphin ring CβCβ+ CmCαstretch, Cm−ph stretch, and simultaneously along the asymmetric ν(CmCα)asand ν(CαCβ)asrelaxation processes leading to Qywhile that for S0→ S2is predominantly along the porphin ring CβCβ+ CmCαstretch and simultaneously along the asymmetric ν(CmCα)as+ ν(CαCβ)asrelaxation processes leading to thermal equilibrium in Qx. The excited state structural dynamics of TAPP determined from RRs shows that internal conversion Bx→ Qyelectronic relaxation occurs in tens of femtoseconds and the short-time dynamics were first interpreted with account of the time-dependent wave packet theory and Herzberg−Teller contributions.