Most chemical reactions promoted by light and using a photosensitizer (a dye) are subject to the phenomenon of luminescence. Redistribution of light in all directions (isotropic luminescence emission) and in a new spectral range (luminescence emission spectrum) makes experimental and theoretical studies much more complex compared to a situation with a purely absorbing reaction volume. This has a significant impact on the engineering of photoreactors for industrial applications. Future developments associated with photoreactive system optimization are therefore extremely challenging, and require an in-depth description and quantitative analysis of luminescence. In this study, a radiative model describing the effect of luminescence radiation on the calculation of absorptance is presented and analyzed with the multiple inelastic-scattering approach, using Monte Carlo simulations. The formalism of successive orders of scattering expansion is used as a sophisticated analysis tool which provides, when combined with relevant physical approximations, convenient analytical approximate solutions. Its application to four photosensitizers that are representative of renewable hydrogen production via artificial photosynthesis indicates that luminescence has a significant impact on absorptance and on overall quantum yield estimation, with the contribution of multiple scattering and important spectral effects due to inelastic scattering. We show that luminescence cannot be totally neglected in that case, since photon absorption lies at the root of the chemical reaction. We propose two coupled simple and appropriate analytical approximations enabling the estimation of absorptance with a relative error below 6% in every tested situation: the zero-order scattering approximation and the gray single-scattering approximation. Finally, this theoretical approach is used to determine and discuss the overall quantum yield of a bio-inspired photoreactive system with Eosin Y as a photosensitizer, implemented in an experimental setup comprising a photoreactor dedicated to hydrogen production.