This paper is devoted to the study of the photochemical processes occurring during hologram formation in a biopolymer, agar doped by chromium(VI). The evolution of both the absorbing chromium species and the polymer allowed elucidating the reactions taking place during irradiation in conditions representative of hologram formation. As previously observed with dichromated poly(vinyl alcohol) (PVA), polymer containing hydroxyl groups as agar, irradiation of dichromated agar provoked a two step reduction of chromium species and the crosslinking of the host polymer. But agar has a rather complex chemical structure and the photoproducts formed along the polymeric chains throughout the photoredox process were different in agar and in PVA. The photostability of the matrix, that has been proven, coupled with the possibility to record good quality holograms, allowed us to propose dichromated agar as a new natural photosensitive biomaterial.