The impact of the electronic structure of a series of 4H-imidazolate ligands in neutral, heteroleptic Cu(I) complexes is investigated. Remarkable broad and strong ligand-dependent absorption in the visible range of the electromagnetic spectrum renders the studied complexes promising photosensitizers for photo-catalytic applications. The electronic structure of the Cu(I) complexes and the localization of photoexcited states in the Franck-Condon region are unraveled by means of UV-vis absorption and resonance Raman (rR) spectroscopy supported by time-dependent density functional theory (TD-DFT) calculations. The visible absorption bands stem from a superposition of bright metal-to-ligand charge-transfer (MLCT) and pi-pi* as well as weakly absorbing MLCT states. Additionally, the analysis of involved molecular orbitals and rR spectra upon excitation of MLCT and pi-pi* states highlights the impact of the electronic structure of the 4H-imidazolate ligands on the properties of the corresponding Cu(I) complexes to avail a toolbox for predictive studies and efficient complex design.