Structural and thermodynamic stabilities of monomers and dimers of trialkylphosphine oxides (TRPO) were studied using quantum chemistry calculations. Density functional theory calculations were carried out and the structures of four TRPO have been determined: TMPO (methyl; R ϭ CH 3 ), TEPO (ethyl; R ϭ CH 3 CH 2 ), TBPO (n-butyl; R ϭ CH 3 (CH 2 ) 3 ), and TOPO (n-octyl; R ϭ CH 3 (CH 2 ) 7 ). TRPO homodimers were investigated considering two isomeric possibilities for each dimer. Relative binding energies and the enthalpic and entropic contributions to the Gibbs free energy were calculated for all dimers. The formation of dimers from the individual monomeric TRPO species as a function of temperature was also analyzed.