In the present study, the structural and electronic properties of hexagonal Sc2B2O2 monolayer (hexa-Sc2B2O2 monolayer) were investigated through density functional theory (DFT)-based first-principles calculations. The material was found to be a semiconductor with an indirect band gap of 0.51 eV. The dynamical stability of the optimized structure was affirmed by phonon band structure calculations. Subsequently, the thermal, electrical, and thermoelectric transport properties of this material were investigated using the Boltzmann transport theory. To illuminate the potential of developing p-type and n-type thermoelectric materials based on hexa-Sc2B2O2 monolayer, the effect of doping on the transport properties was studied within the rigid band approximation. Near-room temperature, the p-type and n-type hexa-Sc2B2O2 monolayers thus obtained demonstrate high-power factors of the order of 102 mWm−1 K−2 and 1 mWm−1 K−2, respectively. Furthermore, the n-type (p-type) materials thus obtained are found to have low (moderate) values of electronic thermal conductivities of the order 10–2 Wm−1 K−1(1 Wm−1 K−1) near-room temperature. These findings suggest the possible potential of hexa-Sc2B2O2 monolayer for near-room temperature thermoelectric applications.