Dimethylformamide (DMF) and a deep eutectic solvent choline chloride-ethylene glycol (ChCl-Eg) were investigated as potential matrix media for static headspace gas chromatographic (SHS-GC) determination of residual solvents in pharmaceuticals. Sample equilibration temperature, equilibration time and injection time were optimized. In the case of DMF 140°C equilibration temperature was applied. For ChCl-Eg equilibration temperature could not exceed 80°C as ChCl-Eg started to degrade at elevated temperatures. The higher equilibration temperature of DMF solutions favoured a transition of the analytes to the headspace and consequently resulted in lower detection limits of the analytes. Thus DMF has been considered a more suitable matrix medium than ChCl-Eg and was applied for the SHS-GC determination of residual solvents in pharmaceuticals.