Abstract Polymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large‐scale hydrogen energy production. Here we show that the palladium/iridium oxide‐loaded homopolymer of dibenzo[b,d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co‐catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co‐catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co‐catalyst.