Spectroelectrochemistry combines the power of spectroscopic analysis with the kinetic, mechanistic and synthetic capabilities of electrochemistry. This presentation will discuss the application of spectroelectrochemical methods to the analysis of redox products drawn from bi- to tetra-metallic complexes, and highlight the insight that can be drawn when such methods are further combined with electronic structure calculations carried out at an appropriate level of theory. This approach has allowed the elucidation of the distinct electronic character of iron and ruthenium mixed-valence complexes featuring all-carbon and carbon-rich bridges, uncovered surprising analogies in the structure-property relationships of weakly-coupled mixed-valence systems and molecular motifs displaying destructive quantum interference, and the truly remarkable electroactivity of tetra metallic tetraethynyl pyrene complexes.