The use of the PBE0 hybrid density functional theory method in conjunction with the COSMO solvation model allowed us to reproduce, both qualitatively and quantitatively, the experimentally observed conformational compositions of 2-substituted and 2,7-disubstituted methylenecyclohexanes. An analysis revealed several different interactions that influence the overall equilibrium. It was found that the endo (general) anomeric effect plays a significant role in the equilibrium and that the "unsaturation effect" possibly comprises two effects.