Six polyoxo-titanium clusters (PTCs) with varying nuclearities containing Ti-N bonds and heteronuclearity, namely, [Ti6(μ3-O)2(μ2-O)2(O3P-Phen)2(OiPr)10(1-hbta)2] (PTC-37), Ti8(μ3-O)2(μ2-O)2(O3P-Phen)2(OiPr)16(adn)2(NO3)2] (PTC-38), [Ti4(μ3-O)(μ2-O)(μ2-OiPr)2(OiPr)4(O3P-Phen)3(1,10-phn)](HOiPr) (PTC-39), [Ti4(μ3-O)(μ2-OiPr)3(OiPr)5(O3P-Phen)3(Im)] (PTC-40), [Ti4(μ3-O)(μ2-OiPr)3(OiPr)5(O3P-Phen)3(Im)][Ti3M(μ3-O)(μ2-OiPr)3(OiPr)3(O3P-Phen)3(Im)] (M = Co for PTC-41 and M = Zn for PTC-42; O3P-Phen = phenyl phosphonate, 1-hbta = 1-hydroxy benzotriazolate, adn = adenine, 1,10-phn = 1,10-phenanthroline, Im = imidazolate, and OiPr = isopropoxide) were prepared as crystalline samples and structurally characterized. Simultaneous doping of nitrogen and transition metal heteroatoms into the Ti-O clusters created complex chemical environments in the resulting hybrid materials. Thus, photocatalytic methylene blue degradation studies were performed to understand structure-property relationships in these Ti cluster-based materials. The complex chemical environment created in these novel molecular clusters had proved to exhibit ligand-dependent photocatalytic activities under normal sunlight. Adenine-functionalized PTC-38 presented moderate activities, while other PTCs all show rapid dye degradation.