Under hydro(solvo)thermal conditions, two 4-(4-carboxyphenoxy)phthalate-based three-dimensional (3-D) coordination polymers: [Cd3(cpph)2(bpa)2(H2O)]·0.5H2O (cpph = 4-(4-carboxyphenoxy)phthalate, bpa = 1,2-bis(4-pyridyl)ethane) 1, and [H2(bpp)][Mn2(cpph)2(H2O)2] (bpp = 1,2-bis(4-piperidyl)propane) 2 were isolated. In both compounds, the cpph molecules extend the metal ions into a 3-D network: a (4,6)-connected net for 1 and a simple 6-connected net with a pcu topology for 2. The introduced bpa or bpp molecule stabilizes the 3-D metal-cpph architecture in the form of linker or guest molecule. The sensing ability of 1 was investigated, revealing that it can be used as a fluorescence probe to sense nitrobenzene at ppm concentrations.