In this work, we designed and synthesized a series of novel heavyatom-free SOCT-ISC photosensitizers based on diehthoxycarbonyl BODIPY scaffold as an electron acceptor. Due to increased electron acceptor ability of diethoxycarbonyl-BODIPY scaffold, dyads with pyrene and anthracene groups as electron donors undergo efficient charge transfer and triplets' formation in non-polar solvent, such as toluene, which is desired for application of these dyes as photoinitiators for polymerization. Transient absorption spectroscopy data confirmed that intramolecular charge separation takes place on the timescale of a few picoseconds followed by recombination of CT states into of triplet excited states of BODIPY via SOCT-ISC. For the lead BODIPY-anthracene compound, excellent photosensitization ability was observed as is evidenced by singlet oxygen generation quantum yields of up to 94%. Diethoxycarbonyl-BODIPY photosensitizers and corresponding reference diiodoBODIPY in combination with NPG have showed the ability to initiate free-radical polymerization of acrylamide monomers under 532 nm irradiation leading to the formation of volume transmission gratings in a cellulose acetatebased photopolymer. The novel heavy-atom-free photosensitizers provide higher exposure sensitivity than a reference heavy-atomcontaining dye, BDPI2. High diffraction efficiency (up to 56%) obtained for CA-PEG layers sensitized with pyrene and anthracene dyads demonstrates that they can efficiently operate as a photosensitizer thus allowing for holographic recording of diffractive structures. The developed photopolymerizable material has low scattering and is capable to achieve the refractive index modulation of up to 2.3 × 10 -3 at the spatial frequency of 800 lines/mm, and good mechanical and chemical stability. The developed photopolymerizable material showed high refractive index modulation, low scattering, and good mechanical and chemical stability. In addition, unchanged diffraction efficiency was observed for 4 months after the recording. These results provide further perspective for the utilisation of heavy-atom-free BODIPYs as components of photoinitiating systems and expand the arsenal of environment-friendly and sustainable photopolymerizable materials for holography applications.