Alkali salts of 1‐hexyl sulfonate were ionized by laser irradiation and the positive ions were analyzed by time‐of‐flight mass spectrometry. The sodium, potassium, rubidium and cesium salts produce relatively simple spectra. The major organic ions observed are due to the salt plus a cation or the dimer plus a cation. No molecular or fragment ions were detected. The instrumentation and the method of interpreting these data are described.