A cobaloxime H2 evolution catalyst with a hydroxo-functionalized pyridine ligand, Co(dmgH)2(4-HEP)Cl [dmgH = dimethylglyoxime, 4-HEP = 4-(2-hydroxyethyl)pyridine] was immobilized on a chromium terephthalate metal-organic framework (MOF), MIL-101(Cr), to construct a MOF-catalyst hybrid which displays good photocatalytic H2 evolution activity. The longevity of the cobaloxime catalyst is increased by MOF incorporation, but limited by the stability of the cobalt-pyridine bond under turnover conditions.