We report a low-temperature colloidal synthesis of single-layer, five-atom-thick, β-In2Se3 nanosheets with lateral sizes tunable from ∼300 to ∼900 nm, using short aminonitriles (dicyandiamide or cyanamide) as shape controlling agents. The phase and the monolayer nature of the nanosheets were ascertained by analyzing the intensity ratio between two diffraction peaks from two-dimensional slabs of the various phases, determined by diffraction simulations. These findings were further backed-up by comparing and fitting the experimental X-ray diffraction pattern with Debye formula simulated patterns and with side-view high-resolution transmission electron microscopy imaging and simulation. The β-In2Se3 nanosheets were found to be indirect band gap semiconductors (Eg = 1.55 eV), and single nanosheet photodetectors demonstrated high photoresponsivity and fast response times.