Methanol in insulating oil has been proposed as a new marker for condition assessment of the solid insulation system of power transformers. In the current work, as a first step of using the new marker, an analytical static headspace gas chromatography/mass spectrometry method has been developed, optimized, and validated to measure methanol and ethanol contents in the insulating mineral oil. The analyzing setup consists of a 6890 N gas chromatograph equipped with a 5973 network mass spectrometer (MS) in the absence of a costly headspace autosampler, and the chromatography separation was performed on a 60 m × 320 µm × 0.5 µm VF-WAXms GC column. Calibration curves have been provided using several concentrations of the alcohols, and also limit of detection (LOD), limit of quantification (LOQ), and relative standard deviation percentage (RSD%) have been determined.