A series of acene-modified zinc porphyrins (benzene to pentacene, denoted as LAC-1 to LAC-5) were prepared to study their absorption spectra, electrochemical properties, and photovoltaic properties. For the absorption spectral changes in THF, porphyrin B bands are red-shifted and broadened from 449 to 501 nm for LAC-1 to LAC-3, showing the effect of additional p-conjugation. In contrast, the B bands of LAC-4 and LAC-5 are blue-shifted. In addition, the tetracenyl group of LAC-4 gives rise to absorption bands in between B and Q bands. On the other hand, the Q bands of LAC-1 to LAC-5 are systematically broadened and red-shifted from 629 to 751 nm. By comparison, the absorption bands of LAC porphyrins on TiO2 films are broadened and slightly shifted. Fluorescence emission maxima of LAC porphyrins in THF are also systematically redshifted from LAC-1 to LAC-5. Cyclic voltammetry experiments in THF/TBAP show that the first reductions are systematically positive-shifted from -1.16 to -0.85 V vs SCE for LAC-1 to LAC-5, indicating the effect of increasing p-conjugation. As for the performance of DSSCs using LAC porphyrins, the overall efficiencies are LAC-1 (2.95%), LAC-2 (3.31%), LAC-3 (5.44%), LAC-4 (2.82%), and LAC-5 (0.10%). Overall efficiency of a LAC-3-sensitized solar cell is nearly twice of that of a LAC-1-sensitized solar cell and is about 81% overall efficiency of N719-sensitized solar cells under the same experimental conditions. The conversion efficiency of incident photons to current (IPCE) experiments shows that the broadened absorption bands of LAC-3 effectively minimizes the gap between B and Q bands, contributing to the improved DSSC performance. The very poor performance of LAC-5 is suggested to be caused by rapid nonradiative relaxation of the molecule in the singlet excited state.