Novel composite ZrO2-Bi2O2(CO)3 (ZrBi) materials were prepared in one step by the chemical co-precipitation method under the same synthesis conditions. Bi2O2(CO)3 was incorporated to ZrO2 adding in 0.5, 1 and 2 mol%. The ZrBi composites were characterized by different techniques: XRD, FTIR, PL, DRS, N2 physisorption, XPS, SEM and HR-TEM. A 50–50% methanol–water solution was used and the results showed that the photocatalytic hydrogen production rate in the ZrBi composites was significantly enhanced when 1 mol% of Bi2O2(CO)3 (ZrBi-1) is added, obtaining a hydrogen production of 8753 µmolH2*g−1. The novelty of this material is that is part microcrystalline and part crystalline, and despite having a band gap energy of 3.9 eV is used without calcining, having considerable energy savings. In addition, oxygen vacancies are observed as well as the presence of heterojunctions between the microcrystalline phase of ZrO2 and the orthogonal structure of Bi2O2(CO3). The presence of heterojunctions and oxygen vacancies increases the transfer of charges, decreasing the probability of recombination of carrier charges (hole-electron pair) and increasing photocatalytic efficiency.