We report first observations of zero-phonon spectral holes in the Soret absorption band of zinc tetraphenylporphyrin (ZnTPP) in polymer matrices with and without electron accepters. The holes are formed by both nonphotochemical and photon-gated photochemical mechanisms. At 4 K there is no evidence of a direct electron transfer from the S-2 state of ZnTPP to an electron acceptor. The electron transfer responsible for the hole formation proceeds via higher triplet states of ZnTPP both in the case of burning in the Soret band and in the case of burning in the Q-band. The zero-phonon hole widths yield the S-2 excited state lifetimes of 0.85-1.6 ps. These values are determined by the internal conversion rates. We observed a marked dependence of the internal conversion rates on the polymer matrix.