Systematic in situ Raman microdroplet spectroelectrochemical (Raman-μSEC) characterization of copper (I) thiocyanate (CuSCN) prepared using electrodeposition from aqueous solution on various substrates (carbon-based, F-doped SnO2) is presented. CuSCN is a promising solid p-type inorganic semiconductor used in perovskite solar cells as a hole-transporting material. SEM characterization reveals that the CuSCN layers are homogenous with a thickness of ca. 550 nm. Raman spectra of dry CuSCN layers show that the SCN− ion is predominantly bonded in the thiocyanate resonant form to copper through its S− end (Cu− S− C≡ N). The double-layer capacitance of the CuSCN layers ranges from 0.3 mF/cm2 on the boron-doped diamond to 0.8 mF/cm2 on a glass-like carbon. In situ Raman-μSEC shows that, independently of the substrate type, all Raman vibrations from CuSCN and the substrate completely …