The nanosecond transient dynamics of N,N,N′,N′-tetramethyl-p-phenylenediamine in poly(methyl methacrylate) has been investigated under ablation condition. Time-resolved spectroscopic data can be interpreted in terms of the dynamics of the lowest excited singlet and triplet states and the cation of TMPD. The decay processes of all the detected transients became rapid with an increase in the laser fluence. It is shown directly that TMPD absorbs about eight 248 nm photons during a nanosecond laser pulse at the ablation threshold of 220 mJ/cm2. These results are well explained by cyclic multiphotonic absorption mechanism where dopant transients work as repetitive absorbers of laser photons.