The self-association equilibrium, i.e. formation of noncovalent dimers, in two triphenylamine derivatives, TPD (N,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine) and mMTDAB (1,3,5-tris[(3-methylphenyl)phenylamino]benzene), in solution was evaluated by 1H NMR spectroscopy. The gas-phase energetics of the respective dimerization processes was explored by computational quantum chemistry. The results indicate that self-association is significantly more extensive in TPB than in TDAB. It is proposed that this fact helps to explain why TPB presents a stability higher than expected in the liquid phase, which is reflected in a lower melting temperature, a less volatile liquid, and possibly a higher tendency to form a glass. These results highlight the influence of self-association on the phase equilibria and thermodynamic properties of pure organic substances.