Here, we report on the first example of crosslinking (CL) hyperbranched polyphenylene (hbPPh) with a small molecule crosslinker 1,3,5-tris(azidomethyl)benzene (TAMB). It was successfully shown that CL of the hbPPh/TAMB (9:1) film is possible either thermally or photochemically making use of fundamentally different reaction mechanisms. Starting from a model reaction to prove the feasibility of the thermal CL reaction, we went on to check both the thermal and the photochemical crosslinkability of micrometer thick films. IR spectroscopy was furthermore used to confirm the CL process. Finally, the thin film morphology of the films before and after CL was investigated by AFM, revealing that the surface morphology was unaffected by the CL processes.