We describe sonication-assisted liquid-phase exfoliation of rhombohedral germanium telluride (α-GeTe) to obtain a good dispersion of α-GeTe nanosheets in ethanol. The thickness of the α-GeTe nanosheets is dependent on the exfoliation conditions, and few-layer α-GeTe nanosheets of 2–4 layers and even monolayer α-GeTe were obtained. We use first-principles calculations to investigate the structural, electronic, and optical properties of monolayer and bulk α-GeTe and compare the optical band gap of centrifugally fractionated α-GeTe nanosheet dispersions with the computational predictions. We demonstrate that few layer α-GeTe nanosheets are purified selectively through centrifugation, and they exhibit high sensitivity to Fe³⁺. The scalable production of two-dimensional α-GeTe nanosheets can be used in the future optoelectronic industry.