The first ambient measurements using nitrate ion based Chemical Ionization with the Atmospheric Pressure interface Time-Of-Flight mass spectrometer (CI-APi-TOF) for sulphuric acid and neutral cluster detection are presented. We have found CI-APi-TOF a highly stable and sensitive tool for molecular sulphuric acid detection. The lowest limit of detection for sulphuric acid was determined to be 3.6 × 104 molecules cm−3 for 15 min averaging. Signals from sulphuric acid clusters up to tetramer containing ammonia were also obtained but these were found to result from naturally charged clusters formed by ion induced clustering in the atmosphere during nucleation. Opposite to earlier studies with cluster mass spectrometers, we had no indication of neutral clusters. The reason is either less efficient charging of clusters in comparison to molecular sulphuric acid, or the low concentration of neutral clusters at our measurement site during these particular nucleation events. We show that utilizing high resolution mass spectrometry is crucial in separating the weak sulfuric acid cluster signal from other compounds.