A novel 3D luminescent coordination polymer (LCP) [Zn4(3-dpyb)2(odpa)2(H2O)3]·4H2O (1) (3-dpyb = N,N'-bis (3-pyridinecarboxamide)-1,4-butane, H4 odpa = 4, 4'-oxidiphthalic acid) was successfully synthesized under solvothermal conditions. LCP 1 displays remarkable fluorescent behavior and stability in a wide range of pH values and different pure organic solvents. More importantly, LCP 1 can become an outstanding candidate in the selective sensing of Fe3+, Bi3+, Cr2O72-, MnO4-, nitrobenzene (NB), acetaldehyde (AH), and acetylacetone (Hacac) under a lower detection limit. The change process of fluorescent intensity of these seven analytes in a diverse pH range indicates that LCP 1 can be an excellent luminescent sensor in multiple acid/base solutions. As far as we know, it is an infrequent example of a CP-based multiresponsive fluorescent sensor for metal cations, oxyanions, and toxic organic solvents under an acid or alkaline environment.