Holographic measurements have shown that the addition of 0.5% of poly(acrylic acid) (PAA) can improve the quality of holograms recorded in poly(vinyl alcohol) (PVA) doped with ammonium dichromate (ADC). The purpose of this paper is to explain this improvement. First, an analytical approach investigated the structural and architectural modification of the polymeric matrix and the fate of the various chromium species within PVA/PAA/ADC films. The addition of PAA in dichromated PVA led to a pre-reticulation of the polymeric matrix. This process increased with the amount of PAA. Second, an analytical approach focused on the evolution of PVA/PAA/ADC films upon irradiation at 365 nm, which is representative of hologram formation. The improvement brought by the presence of 0.5% of PAA in PVA/ADC was assigned to an additional source of crosslinking through the formation of covalent bonds. This process paralleled the crosslinking through coordination bonds involving Cr(V) and PVA units. At 0.5% of PAA, the mobility of the medium before exposure was sufficient to allow the migration of the species involved in the reticulation process during hologram formation, whereas higher concentrations of PAA inhibited this migration.