Sterical (van der Waals-induced) rotational barriers of methyl groups are investigated theoretically, using ab initio and empirical force field calculations, for various three-dimensional microenvironmental conditions around the methyl group rotator of a model neopentane molecule. The destabilization (reducing methyl rotational barriers) or stabilization (increasing methyl rotational barriers) of the staggered conformation of the methyl rotator depends on a combination of microenvironmental contributions from (i) the number of atoms around the rotator, (ii) the distance between the rotator and the microenvironmental atoms, and (iii) the dihedral angle between the stator, rotator, and molecular environment around the rotator. These geometrical criteria combine their respective effects in a linearly additive fashion, with no apparent cooperative effects, and their combination in space around a rotator may increase, decrease, or leave the rotator's rotational barrier unmodified. This is exemplified in a geometrical analysis of the alanine dipeptide crystal where microenvironmental effects on methyl rotators' barrier of rotation fit the geometrical mapping described in the neopentane model.