The wheel‐like tungstophosphate ([P8W48O184]40−, abbreviated as P8W48) reacted with estertin trichloride (Cl3SnRCH3, R = CH2CH2COO) in aqueous solution, resulting in a new wheel‐like polyoxometalate (POM) containing six SnR fragments, formulated as K6Na24[{(SnR(H2O))2(μ‐OH)(μ‐SnR(H2O))}2(P8W48O184)]·59H2O (abbreviated as Sn6‐P8W48). Based on this, the transition metal (TM) was further introduced into the Sn6‐P8W48 system, self‐assembling three other wheel‐like POMs with the general formula KxNayH26 − x − y[{TM(H2O)3(SnR(H2O))2(μ‐OH)(μ‐SnR(H2O))}2(P8W48O184)]·nH2O (abbreviated as TM2‐Sn6‐P8W48, TM = Mn, Co, Ni; x = 0, 1, 2; y = 19, 22, 15; n = 72, 85, 75, respectively). The structures of these new organometal and TM co‐modified compounds were characterized using infrared, UV–Vis. spectroscopy, 119Sn NMR, and powder‐ and single‐crystal X‐ray diffraction analysis. The estertin precursor hydrolyzed into carboxyethyltin (SnR) fragment in these crystalline POM materials, which can improve their adhesion to titanium dioxide (TiO2). The photocatalytic performance of Sn6‐P8W48, TM2‐Sn6‐P8W48, and their TiO2 composites was examined by studying the degradation of a model dye pollutant Rhodamine B (RhB) under visible‐light irradiation without adding hydrogen peroxide (H2O2), and the photocatalytic mechanism was also discussed. The experimental results show that the title compounds exhibit a quicker and better photocatalytic degradation effect on RhB compared with their parent compound, indicating that the introduced organotin groups play a significant role. Moreover, it was found that H2O2 was produced after illumination pretreatment for POM solution, promoting the photocatalytic reaction. [ABSTRACT FROM AUTHOR]