Optical emission spectroscopy is used to investigate trends with changes in processing parameters for Ar/Cu plasmas in an electron‐cyclotron‐resonance (ECR) plasma deposition system. The primary motivation for this work is to monitor trends in ionization fractions for copper deposition plasmas using a noninterfering diagnostic tool. The system, which consists of a solid copper sputter target coupled to a permanent magnet ECR microwave plasma system, is operated in the range of 1–6 mTorr argon with net microwave input power of 500–1500 W. Emission from the following excited states is monitored: Ar neutrals (696.5 nm); Ar ions (488 nm); Cu neutrals (521.8 and 216.5 nm); and Cu ions (213.6 nm). Cu ion emission and Cu neutral emission monotonically increase with net microwave input power but at slightly different rates for different pressures, while argon‐ion emission as a function of pressure shows a broad peak around 4 mTorr. The ratio of Cu ion emission to Cu neutral emission is used as an indicator of the relative ionization efficiency for Cu and peaks near 5 mTorr. Spectroscopic estimates of electron temperature differences between pure Ar and Ar/Cu plasmas are also presented.