In recent research [ Chem. Commun. 2014 , 50 , 8667 ], it was found that photoinduced enolization occurred in 1,9-diformyl-5,5-diaryldipyrromethane (DAKK) by excited-state dual proton transfer resulting in a red-shifted absorption, a phenomena not observed in 1,9-diformyl-5,5-dimethyldipyrromethane (DMKK) and 1,9-diformyl-5-aryldipyrromethane (MAKK). The observation was supported by preliminary density functional theoretical (DFT) calculations. In the work reported here, a detailed and systematic study was undertaken considering four molecules, 1,9-diformyldipyrromethane (DHKK), DMKK, MAKK, and DAKK and their rotational isomers using DFT methods. Different processes, namely, cis-trans isomerization and single and double proton transfer processes, and their mechanistic details were investigated in the ground and excited states. From the simulation studies, it was seen that the presence of different substituents at the meso carbon does not affect the λabs values during cis → trans isomerization. However, enolization by proton transfer processes were found to be influenced by the substituents, as seen in the experiments. Enolization was observed to follow a stepwise mechanism, that is, diketo → monoenol → dienol. While monoenols showed negligible substituent effects on the λabs values, a large red shift in λabs was seen only in DAKK, in agreement with the experimental findings. This observation can be attributed to the lowering of the keto → enol activation barrier, stabilization of DAEE in the S1 state, and the charge transfer nature of the transitions involved in DAEE.