A novel mixed ligand one-dimensional coordination polymer (1D CP), {[Cd2(adc)2(4-nvp)6]·(MeOH)·(H2O)} n (1; H2adc = 9,10-anthracenedicarboxylic acid, and 4-nvp = 4-(1-naphthylvinyl)pyridine), has been synthesized and structurally characterized by single crystal X-ray crystallography. The 1D polymer undergoes supramolecular aggregation via hydrogen bonding, C-H···π, and π···π interactions. Interestingly, compound 1 shows increasing conductivity upon irradiation of light. Therefore, it has the potential to be used in optoelectronic devices. Moreover, the supramolecular assembly of 1 specifically detects Cr3+ cation in the presence of other competitive analytes. Most importantly, compound 1 exhibits fascinating turn-on Cr3+ sensing, which seems to be an ornament in the field of sensing application.