The present manuscript is a conceptual review concerning the photo-Fenton reaction at near-neutral pH, used for bacterial inactivation. In this first Part, an overview of the mechanisms involved, as well as the fundamental concepts governing the near-neutral photo-Fenton reaction are critically assessed. The two constituents of the process, namely solar light and the Fenton reagents, are dissociated, with their direct and indirect actions thoroughly analyzed. The effects of UVB and UVA on the bacterial cell are firstly discussed, followed by the presentation of the indirect oxidative stress-related inactivation mechanisms initiated into the microorganism, in presence of light. Afterwards, the effect of each Fenton reagent (H2O2, Fe) is analyzed in a step-wise manner, with H2O2 and Fe as enhancements of the solar disinfection mode of action. This approach proves that in fact, the solar photo-Fenton reaction is an enhanced solar disinfection process. Finally, the photo-Fenton reaction is put into context by considering the possible interactions of the separate parts of the combined process with the constituents of the natural environment that can play an important role in the evolution of the bacterial inactivation. (C) 2016 Elsevier B.V. All rights reserved.