Microwave has nonthermal effects on enzymatic reactions, mainly caused by the polarities of the solvents and substrates. In this experiment, a model reaction with caprylic acid and butanol that was catalyzed by lipase from Mucor miehei in alkanes or arenes was employed to investigate the nonthermal effect in nonaqueous enzymatic esterification. With the comparison of the esterification carried by conventional heating and consecutive microwave irradiation, the positive nonthermal effect on the initial reaction rates was found substrate concentration-dependent and could be vanished ostensibly when the substrate concentration was over 2.0 mol L(-1). The polar parameter log P well correlates the solvent polarity with the microwave effect, comparing to dielectric constant and assayed solvatochromic solvent polarity parameters. The log P rule presented in conventional heating-enzymatic esterification still fits in the microwaved enzymatic esterification. Alkanes or arenes with higher log P provided positive nonthermal effect in the range of 2 ≤ log P ≤ 4, but yielded a dramatic decrement after log P = 4. Isomers of same log P with higher dielectric constant received stronger positive nonthermal effect. With lower substrate concentration, the total log P of the reaction mixture has no obvious functional relation with the microwave effect.