We demonstrate that the chemical composition of the sputtered CuCl thin films could be finely controlled by adjusting the bias to the substrate. The films deposited without any intentional bias were Cl rich (CuCl1+x), a bias of −22 V yielded stoichiometric CuCl, and a further increase in the negative bias resulted in Cl deficient films (CuCl1−x). The crystalline and optical properties were found to be associated with the chemical composition. Cl rich films showed a deep level green emission at around 515 nm in addition to ultraviolet (UV) excitonic emission. The stoichiometric films have higher optical quality, exhibiting a sharp UV emission at around 385 nm at room temperature, compared to nonstoichiometric samples. Visible luminescence related to deep level defects was not observed in the stoichiometric films. Changes in energy of the flux from the target and the subsequent ion bombardment on the substrate surface are correlated with the variations in chemical composition and their impact on the film microstructure and UV emission.