A series of sulfur-containing hyperbranched polymeric photoinitiators end-capped with benzophenone (BP) and tertiary amine moieties (B/A-HPIs) were synthesized via the simultaneous double thiol-ene click reactions of thiolated hyperbranched polymer with both dimethylaminoethyl acrylate and 3-(4-benzoylphenoxy)propyl acrylate. The molecular structures were characterized by 1H NMR and FT-IR spectroscopy. From the UV–vis spectra, B/A-HPIs showed the stronger n-π* absorption at ∼340 nm with a higher molar extinction coefficients of 371 L mol −1 cm −1 than 148 L mol −1 cm −1 of BP, and an obvious red shift of π–π* absorption from ∼250 nm of BP to ∼280 nm. According to the photo-DSC study, the photopolymerization rate of 1,6-hexanediol diacrylate initiated by 5 wt% B/A-HPI was twice higher than that by BP. The DMTA results showed the good miscibility of B/A-HPIs with acrylate resins and high crosslinking density of cured films.