The efficiency of free radical polymerization by photoinitiating systems based on two Astrazon orange cyanine dyes was shown to be directly related to the isomerization process of the dye in the excited states. The impact of resin viscosity on photopolymerization reactions was measured and related to the overall radical quantum yields. The quantum yields were calculated according to the photocyclic behaviour of the initiating systems based on the Astrazon orange dyes. These dyes are characterized by a viscosity dependent photophysics, which leads to an isomerization-diffusion-controlled photopolymerization. Besides this demonstration, Astrazon orange dyes appeared to be very good candidates for free radical photopolymerization in the visible, presenting high absorption coefficient, low cost and good sensitivity.