A series of complexes with low-energy Fe^II to Ti^IV metal-to-metal charge-transfer (MMCT) transitions, Cp₂Ti(C₂Fc)₂, Cp*₂Ti(C₂Fc)₂, and ^MeOOCCp₂Ti(C₂Fc)₂, was investigated using solvatochromism and resonance Raman spectroscopy (RRS) augmented with time-dependent density functional theory (TDDFT) calculations in order to interrogate the nature of the CT transitions. Computational models were benchmarked against the experimental UV-Vis spectra and B3LYP/6-31G(d) was found to most faithfully represent the spectra. The energy of the MMCT transition was measured in 15 different solvents and a multivariate fit to the Catalán solvent parameters – solvent polarizability (SP), solvent dipolarity (SdP), solvent basicity (SB), and solvent acidity (SA) – was performed. The effect of SP indicates a greater degree of electron delocalization in the excited state (ES) than the ground state (GS). The small negative solvatochromism with respect to SdP indicates a smaller dipole moment in the ES than the GS. The effect of SB is consistent with charge-transfer to Ti. Upon excitation into the MMCT absorption band, the RRS data show enhancement of the alkyne stretching modes and of the out-of-plane bending modes of the cyclopentadienyl ring connected to Fe and the alkyne bridge. This is consistent with changes in the oxidation states of Ti and Fe, respectively. The higher-energy transitions (350–450 nm) show enhancement of vibrational modes consistent with ethnylcyclopentadienyl to Ti ligand-to-metal charge transfer (LMCT). The RRS data is consistent with the TDDFT predicted character of these transitions. TDDFT suggests that the lowest-energy transition in Cp₂Ti(C₂Fc)₂CuI, where CuI is coordinated between the alkynes, retains its Fe^II to Ti^IV MMCT character, in agreement with the RRS data, but that the lowest-energy transitions have significant CuI to Ti character. For Cp₂Ti(C₂Fc)₂CuI, excitation into the low-energy MMCT absorption band results in selective enhancement of the symmetric alkynyl stretching mode.