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Formation of singly and doubly charged Arq+ and Tiq+ (q = 1,2) and of molecular Ar 2 +, ArTi+, and Ti 2 + ions in a direct current magnetron sputtering discharge with a Ti cathode and argon as working gas was investigated with the help of energy-resolved mass spectrometry. Measured ion energy distributions consist of low-energy and high-energy components resembling different formation processes. Intensities of Ar 2 + and ArTi+ dimer ions strongly increase with increasing gas pressure. Addition of oxygen gas leads to the formation of positively charged O+, O2 +, and TiO+ and of negatively charged O− and O2 - ions.