In this study, novel photocurable biobased and biodegradable composites with functionalized fillers from industrial inorganic waste have been developed and applied in optical 3D printing technology. Hydrothermally synthesized calcium silicate hydrates from aluminium fluoride production waste were used as fillers in photoresins based on acrylated epoxidized soybean oil-based. The use of fillers synthesized from industrial waste led to an improvement in the mechanical properties of polymer composites compared to filler synthesized from impurity-free material. The high 3D printing accuracy, perfect layer adhesion, and smooth surface finishing of 3D objects printed with a commercial digital light processing (DLP) 3D printer were shown by the developed composites. The biodegradability of photocured polymer composites reached 19.6% in 60 days. The developed composites have the great potential to be a competitive alternative to conventional petroleum-derived ones and reduce the environmental impact.