This study describes a facile one-pot solvothermal method for the synthesis of heterostructured (HS) Bi2S3–TiO2 (BT) nanoparticles (NPs) and utilizes its potential for sensing the nitrobenzene (NB) as a fluorescent probe. The characterization of as-synthesized BT NPs endorses the mixed morphology with an average particle size of 14[Formula: see text]nm and the crystallography study depicted the orthorhombic Bi2S3 and tetragonal anatase TiO2 phases. The selectivity and sensitivity of BT NPs toward NB were examined by comparing the fluorescence quenching with a few other selected organic aromatic compounds. The appreciable quenching efficiency of 97% was achieved with NB. The visual response of the BT/NB mixture was noticed under UV light ([Formula: see text][Formula: see text]nm). The quenching parameters of the BT/NB system have been evaluated by modifying Stern–Volmer and double logarithmic equations. The results attribute the prevalence of dynamic quenching within the concentration range (0.4[Formula: see text]mM to 5[Formula: see text]mM) and beyond 5[Formula: see text]mM, both static and dynamic quenching coexist. Further, thermodynamic studies of the BT/NB system indicate the spontaneous hydrophobic interaction. Moreover, a reliable outcome has been demonstrated in the sensing application of BT NPs in real water samples.