The spectroscopic and photophysical properties of a typical dithiobenzoate reversible addition-fragmentation chain transfer (RAFT) polymerization agent alone in solution, as a quencher of electronically excited acenaphthene in solution, and in an acenaphthene donor–dithiobenzoate acceptor dichromophore have been investigated. The RAFT agent is an effective quencher of photo-excited acenaphthene. Energy wastage in the dichromophore occurs by Förster resonant electronic energy transfer from the S1 state of acenaphthene to the S2 state of the dithioester, which subsequently fragments.