The linkage of PO43− and HAsO42− anions with a newly synthesized five-coordinate dinuclear zinc complex, [Zn2(cpdp)(H2O)2]Cl (1) [H3cpdp=N,N′-bis[2-carboxybenzomethyl]-N,N′-bis[2-pyridylmethyl]-1,3-diaminopropan-2-ol], has been explored. In methanol–water, the reaction of 1 with Na2HPO4·2H2O and Na2HAsO4·7H2O/NaBr separately, at ambient temperature, yielded the novel phosphate-bridged decanuclear zinc cluster, (H3O)4[Zn10(cpdp)4(μ5-PO4)2(H2O)6](6Cl)·53H2O (2) and hydrogen arsenate-bridged tetranuclear zinc cluster, Na2[Zn4(cpdp)2(μ4-HAsO4)]ClBr·13H2O (3), respectively. Analysis of the single crystal X-ray structure discloses that the metallic core of cluster 2 entails eight distorted trigonal bipyramidal and two distorted octahedral zinc ions, displaying a μ5:η2:η1:η1:η1 bridging mode of two PO43− groups. The metallic core of cluster 3 holds four distorted trigonal bipyramidal zinc ions, showing a μ4:η1:η1:η1:η1 bridging mode of the HAsO42− group. In solution, UV–Vis titration spectra of complex 1 upon increasing the concentration of the PO43− and HAsO42− anions show a significant binding-induced increase in the absorption intensities of 1, accompanied by a substantial red shift. Additionally, the integrity of all three zinc assemblies has been confirmed by 1H and 13C NMR spectroscopic data in solution. The thermal behaviors of 1, 2 and 3 have been studied by thermogravimetric analysis (TGA).