High-pressure Diels-Alder cycloaddition reaction of fullerenes is an important synthetic method for the thermally stable cycloadducts. The effects of high pressure on the potential energy surfaces of Diels-Alder cycloaddition of cyclopentadiene and C60 were studied with a recently developed approach, the polarizable continuum model for extreme pressure (XP-PCM). It is revealed that the high pressure reduces the activation energies and increases reaction energies drastically, making the DA reaction more favorable. The pressure effects on the reaction energetics can be divided into the cavitation and electronic contributions. For the activation energy, the cavitation contribution is significant in comparison with the electronic contribution. To assist future experiments, the activation volume and reaction volume were computed on the basis of the relationship between activation energy or reaction energy with the pressure as a consequence of the fitting linear correlation between activation energy or reaction energy with the pressure.