To fabricate highly efficient dye sensitizers for dye-sensitized solar cells, new zinc porphyrin dye sensitizers were designed based on one of the most efficient dyes, YD2-o-C8, by introducing electron-rich heterocyclic rings into the electron donor. Five potentially efficient dyes, Dye1–5, were obtained by replacing the phenyl group of the donor in YD2-o-C8 with pyrrolyl, furyl, and thienyl groups. The electronic structures, absorption spectra, intramolecular charge-transfer characteristics, and excited-state lifetimes of the designed dyes were investigated using the density functional theory and time-dependent density functional theory methods. All the designed dyes exhibit better photoelectric properties than those of YD2-o-C8. Compared with YD2-o-C8, the designed new dyes have smaller frontier molecular orbital energy gaps and obvious red-shifting absorption spectra in the Q band. The analyses of charge density difference plots and intramolecular charge-transfer characteristics indicated that the designed dyes can better promote intramolecular charge transfer and electron–hole separation. Among the five designed dyes, Dye1 with a pyrrolyl group exhibits the best performance. Dye3 and Dye5 with methyl-furyl and methyl-thienyl groups, respectively, exhibit the next best performance. Dye2 and Dye4 with furyl and thienyl groups, respectively, are the worst performers. The introduced methyl group can further improve the electron-donating ability of heterocyclic rings and promote the red shift of the Q bands and intramolecular charge transfer of dyes. The excited-state lifetimes of the new dyes were in the following order: YD2-o-C8 < Dye4 < Dye2 < Dye5 < Dye3 < Dye1, which shows their stronger abilities to inject electrons into semiconductor films.