An ion-trap/time-of-flight mass spectrometer in combination with an atmospheric pressure sampling interface was developed in order to simultaneously profit from the ease of sample handling at ambient pressure, from the storage and accumulation capabilities of an ion trap, and from the acquisition speed and sensitivity of a time-of-flight mass spectrometer. The sampling interface is an intermediate-pressure vacuum manifold that serves to enrich sampled analytes by jet separation with respect to the carrier gas ͑air͒ and simultaneously maintain vacuum conditions inside the ion-trap/ time-of-flight instrument. Neutral analyte molecules are sampled and later ionized either by electron impact or chemical ionization. Ion accumulation is performed with a rf-only quadrupole ion trap with ground potential on the end caps during storage. For mass analysis, the trap's electrodes serve as a pulsed ion source for the attached linear time-of-flight mass spectrometer. In addition, laser desorbed molecules can also be sampled with this kind of instrument. Successful operation is shown by analyzing volatile substances ͑aniline, bromobenzene, styrene, and perfluorotributylamine͒, as well as laser-desorbed organic solids. Figures of merit include a sensitivity of 10 ppm, resolving power of 300 and demonstration of a mass spectrum of laser-desorbed anthracene with a signal-to-noise ratio of 270.