Intensive effort to tailor photophysics of lead-free perovskites is appealing in recent years. However, their combined electronic and optical property elucidations remain elusive. Here, we report spectroscopic observations of the coexistence Zhang-Rice singlet state and exotic electronic transitions in two-dimensional copper-based perovskites. Herein, several perovskites with different alkylammonium spacers are investigated to unravel their correlated electronic systems and optical responses. Namely, methylammonium, ethylammonium, phenylmethylammonium and phenethylammonium. Using temperature dependent high-resolution X-ray absorption spectroscopy, we observe distinct electronic features highlighting the impact of short spacer chains compared to long-conjugated ligands, demonstrating a pronounced 3d⁹ and 3d⁹L signature linewidth variation. Corroborated by density functional theory calculations, the transient dynamics evolution of copper-based hybrid perovskites is influenced by the strong interplay of electron-phonon interactions and geometric constrictions. This finding sheds light on tuning the electronic and optical properties of hybrid perovskites towards efficient photoactive-based devices.