The quality of the films obtained by magnetron sputtering depends on numerous parameters, including the energy of the ions impinging on the substrate. The energy distribution functions of Ar and Ag ions during magnetron sputtering of a silver target in rf argon plasmas are hereby reported. Measurements were carried out by plasma sampling mass spectrometry at (i) various bias voltages on the surface of the target at constant pressure and (ii) various operating pressures at constant bias voltage. A distinct high-energy tail is observed for the sputtered silver ions (ionized in the plasma) in comparison to the argon gas ions. The results indicate that the sputtered Ag atoms are not completely thermalized by collisions with background gas atoms over the range of experimental conditions investigated. To confirm such assertion, a model has been developed for the ejection of Ag atoms from the target, their transport in the gas phase, and their acceleration in the sheath at the surface of the mass spectrometer. Since sputtering occurs at low impinging ion energies, the energy distribution function of the extracted atoms cannot be represented by the usual Sigmund–Thomson distribution. It is rather assumed to be characterized by a bi-Maxwellian distribution, with one population related to the direct “classical” sputtering and the other one to indirect “2-step etching.” During the transport of Ag neutrals, both ionization and thermalization processes are considered. Finally, the rf sheath near the entry of the mass spectrometer oscillates at a period close to the transit time of the ions passing through it. This induces a complex energy gain also implemented in the model. An excellent agreement between the latter and experimental measurements is obtained. The results are used to probe the effect of the bias voltage and pressure on the fitting parameters, namely, the dc and rf components of the voltage drop in the sheath, the mean energy of the sputtered atoms, and the relative importance of the sputtered populations.