Hydroarylation of cinnamic acid with different substituted phenols, in the presence of acidic ionic liquid, N-methyl-2-pyrrolidonum hydrosulfate ([H-NMP]HSO4) gave the corresponding dihydrocoumarins in high yields and excellent selectivity. Among these substituted phenols, while methyl phenol afforded the corresponding dihydrocoumarin, nitrophenol under the same reaction conditions diverted the course of reaction, affording 3-(4-nitrophenyl)-3-phenylpropanoic acids. We investigated this behavior from the energetic and electronic points of view, using quantum chemistry computational methods. In this respect, the electronic energy change values for the conversion reaction of substituted phenyl cinnamate esters to dihydrocoumarin compounds have been obtained via density functional theory calculations. We demonstrated that the conversion reaction in the presence of CH3 substituent is more favorable energetically than NO2 substituent. Moreover, we have concentrated on topological analysis of electron density on some key bond and ring critical points and their associated bond paths to assess the conversion of substituted phenyl cinnamate esters to dihydrocoumarins. Our calculated results showed that para-methyl phenyl cinnamate has more of electronic tendency to undergo the intramolecular cyclization step and, consequently, generate the corresponding dihydrocoumarin.