The spectroscopic properties and photopolymerization activities of a mono- and tetraperester derivative of benzophenone are examined and compared with those of benzophenone. Their photopolymerization activity in methyl methacrylate (MMA) and an ethoxylated bis-phenol-A diacrylate have been studied using a combination of gel permeation chromatography (GPC), and real time Fourier transform infrared spectroscopy (RTFTIR) as well as the commercial pendulum hardness test. Using GPC analysis on the poly(methyl methacrylate) samples the tetra--t-butyl perester derivative of benzophenone is found to give a higher weight average (Mw) and number average (Mn) molecular weight polymer than that produced using the mono perester. For the two peresters of benzophenone photopolymerization efficiency using real time FTIR increases with increasing initiator concentration, and no self-termination is observed up to 0.75% w/w concentration with the mono perester derivative being the more efficient initiator. Similar results were obtained using the commercial pendulum hardness tester with a triacrylate/epoxyurethane acrylate resin with benzophenone exhibiting the lowest activity. Photopolymerization activities of the initiators correlate well with their spectroscopic properties. The phosphorescence quantum yield is higher for the monoperester than the tetraperester derivative and is consistent with a shorter lifetime and lower photolysis quantum yields in 2-propanol. Compared with benzophenone, phosphorescence analysis indicates that the perester groups impart a degree of charge-transfer content to the molecule which is consistent with the degree of substitution. Ketyl radical formation on microsecond flash photolysis follows the order benzophenone > mono- > tetraperester derivative and is consistent with the phosphorescence quantum yields. On nanosecond laser flash photolysis in nitrogen-saturated acetonitrile, triplettriplet absorption is extremely weak for both the perester derivatives, being stronger for the monoperester.