Three ZnII and CdII complexes with Y‐shaped dicarboxylate ligands, namely [Zn(L1)(2,2′‐bpy)2(H2O)]·2H2O (1), [Zn(L1)(bpp)(H2O)] (2), and [Cd(L1)(H2O)]·H2O (3) [H2L1 = N‐phenyliminodiacetic acid, 2,2′‐bpy = 2,2′‐bipyridine, bpp = 1,3‐bis(4‐pyridyl)propane] were synthesized and characterized by elemental analysis, IR spectroscopy single‐crystal X‐ray diffraction, and thermogravimetric analyses. Compound 1 shows an hydrogen‐bonded 2D network, whereas compound 2 is an infinite 1D wavy chain structure, though O–H···O hydrogen‐bonded to form a 2D network. Compound 3 displays a 2D uninodal 3‐connected Shubnikov plane net with the point symbol of (4.82). Moreover, the solid‐state such as thermal stabilities and fluorescence properties of 1–3 were also investigated.