Titanium disilicide (TiSi2) is a high-melting compound with excellent conductivity, which appears to have potential applications in field-emission. In the present article, TiSi2 thin film was successfully synthesized on a silicon wafer through an in situ chloride-generated strategy by atmospheric-pressure chemical-vapor deposition. The required titanium chloride-precursor vapor was in situ produced at an elevated temperature by preloading NiCl2∙6H2O onto Ti powder with anhydrous ethanol. This synthetic strategy avoided inconvenience with the direct usage of titanium halide or titanium powder as delivering gaseous precursors. The field-emission behavior of the sample shows a turn-on field of 7.2 V/μm and agrees well with the conventional Fowler–Nordheim theory. No obvious degradation was observed in a life-stability experiment period for over 100 min. The convenient and low-cost preparation of the TiSi2 thin film and its fine field-emission performance suggest that it can serve as a good candidate for a field emitter.