Phenalenyl and a wide variety of its derivatives form stable radicals, which often associate in various aggregates with interesting properties that include magnetism and high electrical conductivity. The two main modes of aggregation involve p-stacking pancake multicenter bond formation and s-bond formation. We explore the energetics of the various s- and p-dimers for six phenalenyl derivatives with both computational and experimental methods. A modern density functional theory (M05-2X) is used to survey the potential energy surface revealing the mechanism of the aggregation. In order to enrich experimental data, the triphenyl and trimethyl derivatives are newly prepared and their aggregation behaviors are investigated by various analytical methods including ESR, H-1 NMR, UVvis, and single-crystal X-ray diffraction. The agreement between computations and experiments are very good forming the basis of describing trends in this series. We find that p-dimer formation can proceed via an asynchronous concerted path from the monomers or in a stepwise process via s-dimers. The strength of the p-stacking pancake interaction depends strongly on substituents and covers a wide range both in terms of binding energies and contact distances. The spin densities in the p-stacking dimers reflect these trends and display a wide range of diradicaloid characters. Many s-dimer configurations compete some of which are separated by small barriers leading to fluxional structures between sigma-bonded configurations or s- and pi-bonded configurations.