We have identified a donor-acceptor TADF compound that can perform competitively in a range of photocatalytic reactions with the commonly used 4CzIPN, encompassing a variety of different mechanisms. In particular, the high triplet energy of pDTCz-DPmS permitted the selective and efficient E/Z isomerization of high triplet energy substrates. The much-improved photostability of pDTCz-DPmS relative to 4CzIPN under the reaction conditions investigated presents an additional advantage of this compound. As such, our study shows that TADF donor-acceptor compounds beyond 4CzIPN and the CDCB family can not only be employed but can perform even more efficiently than this popular organic photocatalyst.