The outcome of photosensitized [2+2]-cycloaddition reactions of various cinnamates has been compared in different reaction media, including homogeneous organic solutions under inert conditions, degassed water, and aerated physical gels. The reactions were performed under LED blue light (lambda(max)=455 nm) irradiation and [Ir{dF(CF3)ppy}(2)(dtb-bpy)]PF6 (1.0 mol%) as photocatalyst. The processes were optimized taking into consideration solvent, gelator, and substrate. Comparative kinetics analyses, as well as the effect of the reaction media on the diastereoselectivity of the process, were evaluated during this investigation. In a number of cases, carrying out the reaction in a less polar solvent, like toluene or highly polar solvent, like water had a tremendous impact on the diastereoselectivity of the process, pointing towards an effect on the stabilization of the putative diradical intermediate in this medium. Moreover, while for reactions run in homogeneous solution oxygen needs to be excluded, no erosion in yield is observed when the photoadditions were run in aerated gel media.