The dark photon is a hypothetical gauge boson arising in extensions of the Standard Model, and has emerged as a compelling dark matter candidate. As dark photon dark matter (DPDM), it can interact with electromagnetic fields via kinetic mixing, and the inelastic scattering process γA'e+e- becomes kinematically allowed for gamma rays above a characteristic energy threshold. This interaction imprints unique spectral attenuation features at very-high-energies (VHE), offering an observational probe of DPDM models. Using the Cherenkov Telescope Array Observatory (CTAO) Instrument Response Functions (IRFs), we simulate observations of VHE sources and forecast novel sensitivities to the kinetic mixing parameter for the photon-dark photon scattering process. Our study focuses on three key astrophysical targets: the Crab Nebula and the blazars Markarian 421 and Markarian 501. Additionally, we investigate the impact of dark matter spikes around black holes on the upper limits. For the dark matter spike scenario considered in this work, CTAO observations could probe the DPDM parameter space down to a mixing parameter of ε ∼ 10-8 for masses around mA' ∼ 10-1 eV through high-energy spectral attenuation, at a 95% confidence level.