A series of cross-linked materials was prepared via photo-induced reactions involving olefin-containing precursors and dithiols. The resultant materials (M1–M6) combine conventional feedstock with biobased ones and allow to forge hybrid thermosets whose properties were investigated by a range of analytical methods. Materials M1 and M2 served as references to compare with the biohybrid ones (M3–M6), whose thermal, spectra and mechanical properties can be easily regulated by the type of bio-component added to the overall composition. The biobased compositions allowed to expand the range of thermal properties and the degree of stiffness as measured by TGA, DSC and DMA, with the overall material morphology not being significantly altered as evidenced by SEM.