We have reported CuS microcloves (MCs) for highly selective detection of benzene using scanning kelvin probe (SKP) technique. The electron microscopy investigations revealed the formation of clove shaped CuS with a size of about 1–2 µm at 180 °C and 6 h. The time of reaction significantly affected the crystallinity as well as the morphology of resulting CuS materials. The investigations on adsorption behavior of different types of common volatile organic compounds (VOCs) with varying charge and nature revealed an outstanding selectivity towards benzene when compared to other VOCs. The difference in work function between gold tip and sensor surface modified with CuS MCs was decreased under the exposure of light, most likely caused by transfer of electrons to conduction band of CuS under illumination of light. As a result, the CuS MCs showed enhanced photo response in visible light exposure in the presence of benzene. A chemiresistive type sensor device was fabricated using CuS MCs and exposed to benzene vapor in a concentration ranging from 2.8 to 11.2 ppm. The sensitivity was found to be 1.63 × 10-3 ppm−1. Notably, a rapid response time of ∼6 s and recovery time of ∼ 16 s was achieved for the sensor at a benzene concentration of 5.6 ppm at room temperature. Also, considerable and repeatable sensor response was observed for 560 ppb of benzene vapor at 70 °C. Hence, these results suggested that the CuS MCs have huge potential as novel material for selective benzene detection in gas phase towards breath analysis and other environmental monitoring.