Recurrent selection has been reported as successful for improving maize resistance against corn borers. This study was conducted to determine if phenolics concentration in maize changes during recurrent selection to improve stalk resistance to the Mediterranean corn borer. Three cycles of selection [EPS12(S)C0, ESP12(S)C2, and EPS12(S)C3] from the maize synthetic population EPS12 and test crosses to inbred lines A639, B93, and EP42 were field grown and artificially infested with Mediterranean corn borer larvae, and the pith tissues were sampled for biochemical analyses. Two major simple phenolic acids [p-coumaric (p-CA) and trans-ferulic (E-FA) acids] were identified in free and cell-wall fractions, whereas four isomers of diferulic acid (DFA) (8-5'l, 5-5', 8-o-4', and 8-5' benzofuran form) were present in the cell-wall bound fraction. The selection cycles EPS12(S)C0 and EPS12(S)C3 showed less damage and higher cell wall phenolics concentrations than the cycle EPS12(S)C2. In addition, higher concentrations of total DFAs were associated with shorter tunnel length and lower numbers of larvae per stem. The current study shows new and concrete evidence that the cell-wall bound phenolics could have a determinative role in the resistance to the Mediterranean corn borer, although future development of recurrent and divergent selection cycles will clarify this point.