Hydrogen boride (HB) sheets are metal-free two-dimensional materials comprising boron and hydrogen in a 1:1 stoichiometric ratio. In spite of the several advancements, the fundamental interactions between HB sheets and discrete molecules remain unclear. Here, we report the adsorption of CO2 and its conversion to CH4 and C2H6 using hydrogen-deficient HB sheets. Although fresh HB sheets did not adsorb CO2, hydrogen-deficient HB sheets reproducibly physisorbed CO2 at 297 K. The adsorption followed the Langmuir model with a saturation coverage of 2.4 × 10−4 mol g−1 and a heat of adsorption of approximately 20 kJ mol−1, which was supported by density functional theory calculations. When heated in a CO2 atmosphere, hydrogen-deficient HB began reacting with CO2 at 423 K. The detection of CH4 and C2H6 as CO2 reaction products in a moist atmosphere indicated that hydrogen-deficient HB promotes C–C coupling and CO2 conversion reactions. Our findings highlight the application potential of HB sheets as catalysts for CO2 conversion.