In this work, a copper iodine module bearing a coordination polymer (CP) with a formula of [(Cu2I2)2Ce2(INA)6(DMF)3]·DMF (1, HINA = isonicotinic acid, DMF = N,N’-dimethyl formamide) is presented. The title compound features a three dimensional (3D) structure, in which the {Cu2I2} cluster and {Cu2I2}n chain modules are coordinated by N atoms from a pyridine ring in INA− ligands, while the Ce3+ ions are bridged by the carboxylic groups of INA− ligands. More importantly, compound 1 exhibits an uncommon red fluorescence (FL) with a single emission band maximized at 650 nm belonging to near infrared (NIR) luminescence. The temperature dependent FL measurement was applied to investigate the FL mechanism. Remarkably, 1 could be used as a FL sensor to cysteine and the nitro-bearing explosive molecule of trinitropheno (TNP) with high sensitivity, demonstrating its potential FL sensing applications for biothiol and explosive molecules.