Sacrificial electron donors are frequently used in photocatalytic reactions to enhance the performance of the reaction, typically short-chain alcohols as well as their respective aldehydes and acids are used. This study focuses on the differences between the individual electron donors regarding their oxidation rates, mechanistic pathways, the influence of the intermediates and their direct impact on the H2O2 generation. The individual H2O2 formation rates of 16 different electron donors, photonic and faradaic efficiencies for H2O2 production are carefully discussed. Furthermore, a new multi-reaction pathway for t-butanol oxidation is postulated and critically examined.