A series of perylene-based donor-acceptor-donor (D-A-D) compounds, 3,9-Bis(p-(R)-diphenylamino)perylene (R: CN (2a), F (2b), H (2c), Me (2d), and OMe (2e)), were synthesized using 3,9-dibromoperylene with p-(R)-diphenylamine, and the intramolecular charge transfer (ICT) on the D-A-D system with regards to the electron push-pull substituents effect was investigated. By introducing various p-(R)-diphenylamine derivatives with electron-donating or electron-withdrawing R groups, the energy band gaps of the D-A-D compounds were systematically controlled, and the emission colors were efficiently tuned from green to red. As expected, the steady state emission spectra of all D-A-D compounds were observed, as well as the emission color being controlled, depending on the Hammett substituent constants (σp). In the Lippert-Mataga plots, the different charge transfer character was observed depending on the electron push-pull substitution, which showed gradually increased ICT characters from the electron-withdrawing to donating substitution. However, exceptionally, the strong electron withdrawing group of CN substituted 2a did not correlate with the other R group compounds. From the experimental data and DFT calculations, we assume that there is a constraint on emission color tuning to make higher energy of blue emission in the D-A-D molecular system, due to the reverse charge transfer property caused by the strong electron withdrawing group.