Replicating literature studied photocatalysis reactions is not without issues. The variation in photoreactor set-up means that a yield reported using one photoreactor may not be representative of the yield achieved using an alternative set-up. As such, it is imperative that benchmarking of literature reactions using a consistent photoreactor setup be conducted to permit an accurate comparison of performance. In our case, we observed a background reaction in the absence of PC, despite the report of none existing. This C(sp)-C(sp 3 ) cross-coupling reaction can be promoted either photocatalytically (pDTCz-DPmS) or using a sacrificial photoreductant (HE), substantiated by Stern-Volmer quenching studies. Moreover, the greatest product yield occurs when these mechanistic pathways work in tandem, something that is rarely identified in the photocatalysis literature. This study provides important lessons to the photocatalysis community to always consider testing for background reactions, even when the literature reports none, to carefully assess the potential of each reagent to quench the excited state of the PC and to corroborate reaction yields with relative quenching kinetics.