AbstractTrianthrylene compounds with film‐forming capabilities were synthesized in a three‐step procedure by means of transition‐metal catalyzed Grignard and Suzuki coupling reactions. Upon UV exposure, photopolymerization of the model compound 1,11‐di‐(9‐anthryl)undecane was observed in solution as well in the film due to [4+4] cycloaddition of the anthracene moieties. The soluble photopolymers were characterized by NMR spectroscopy and GPC analysis. As expected, irradiation of solutions of the trichromophoric hydrocarbons afforded crosslinked photoproducts which precipitated from solution. In the case of an analogous trianthryl derivative with tetraoxyethylene spacers, formation of a gel was observed due to cycloaddition of the anthracene groups. The film‐forming capabilities of trianthryl compounds in conjunction with UV‐induced photocrosslinking can be useful for photoresist applications and will be discussed in the foll