Monodispersed, octahedral-shaped CuSe₂ particles were first prepared by an air pressure polyol solution process using triethylene glycol as the solvent, triethylenetetramine as the assisting agent and polyvinylpyrrolidone as the capping agent. The influence of the triethylenetetramine addition and synthesis temperature were investigated, and the products were characterized by XRD, FESEM, SAED, Raman, UV-Vis-NIR and XPS measurements.