The synthetic, thermodynamic and structural investigations of organoruthenium complexes of the form Cp*Ru(triene)OTf (Cp*=n5-(CH3)5C5; triene=anisole 1, indole 2, cycloheptatriene 3, OTf=OSO2CF3) are presented in this contribution. A direct entryway into the thermochemistry of these complexes is made possible by the rapid and quantitative arene/triene substitution for the three acetonitrile ligands in Cp*Ru(CH3CN)3OTf. The solution calorimetric study establishes the following order of stability: cycloheptatriene < anisole < indole. This study helps clarify the enthalpic and entropic components to the thermodynamic driving forces behind the formation of ruthenium arene/triene complexes. The solid-state structures of these three complexes(1–3) were determined by X-ray single-crystal studies. Thermodynamic factors affecting the Ru-triene bond energy are compared with structural results for these three ruthenium complexes.