The potential of the relative sensitivity method was assessed for the direct analysis of solid samples using time-of-flight mass spectrometry with pulsed glow discharge ionization in a combined hollow cathode. Relative sensitivity factors of sample elements were obtained for various samples (copper, steel, nickel, lead, and silicon). For the majority of elements, these factors appeared to be close to unity. The factors were compared with the similar data obtained for direct current (DC) glow discharge; the range of factors obtained in the present work was significantly narrower. This opens up new prospects for pulsed gas-discharge ionization in semiquantitative analysis without using certified reference samples strictly corresponding to the test sample in composition and structure.