The formation of the electron distribution function (EDF) in the bulk plasma of a capacitively coupled radio-frequency (rf) discharge in argon generated in the plasma-chemical reactor PULVA-INP is investigated experimentally and theoretically. Measurements of the EDF and internal plasma parameters were performed by means of a Langmuir probe at pressures of 0.5–100 Pa and discharge powers of 5–100 W. The observed EDFs have revealed a two-temperature behaviour at low pressures and evolved into a Maxwellian distribution at high gas pressures and large discharge powers. Theoretical determination of the EDF is based on the numerical solution of the Boltzmann kinetic equation in the local and non-local approaches under experimental conditions. The model includes elastic and inelastic electron–atom collisions and electron–electron interactions. Low electron temperatures and relatively high ionization degrees are the features of the PULVA-INP rf discharge. This leads to significant influence of the electron–electron collisions on the EDF formation. The modelled and measured distributions show good agreement in a wide range of discharge parameters, except for a range of low gas pressures, where the stochastic electron heating is intense. Additionally, mechanisms of the EDF formation in the dc and rf discharge were compared under similar discharge conditions.