The first thermoelectric (TE) properties of simple polyol method-synthesized Cu 1−x Bi x S (x = 0, 0.02, 0.04, 0.06) nanosheets are reported here. Various characterizations like Rietveld-refined X-ray diffraction (XRD), Raman spectroscopy, Xray photoelectron spectroscopy (XPS), and energy-dispersive X-ray (EDAX) data analysis confirm their single-phase nature of hexagonal crystal structure with space group P63/mmc, stoichiometric nature, valence states of the elements, and nominal elemental composition. Field emission scanning electron microscopy (FESEM) images show nanosheets (NSs) with an average thickness of 27 nm. The doping of Bi atoms in the CuS lattice has been evident from the systematic increase in its crystallite size, optical band gaps, photoluminescence peak intensities, Seebeck coefficients, resistivity, thermoelectric power factors (PFs), and thermoelectric figure of merits (ZTs) with increasing x. The selected area electron diffraction (SAED) pattern confirms that nanosheets are single crystalline in nature. Fourier transform infrared (FTIR) data confirms the absorption bands of the sulfides. The value of the Seebeck coefficient increases with increasing x without deteriorating the electrical conductivity too much due to the energy-dependent scattering of the carriers at the interfaces and the modulation doping. An enhancement of 231% in the thermoelectric power factor and a 6-fold increase in ZT, both at 300 K for x = 0.06 compared to x = 0, are found that show interesting outcomes for these toxic-and rare-earth element-free TE materials.