RATIONALE Ambient sampling and ionization techniques have been attracting attention in imaging mass spectrometry because they offer the advantage of rapid testing. We have developed a method which exploits the fluid motion of charged solvents for both local sampling and ionization with a single vibrating capillary probe. METHODS The capillary probe was used to supply solvents in order to form a liquid bridge between the probe and a sample surface. A bias voltage was applied to the solvents to generate electrospray ionization (ESI). The probe was also vibrated by either an ultrasonic transducer fixed at the back of the sample (contact‐mode) or spontaneous vibration of probe itself (tapping‐mode). The ions generated by ESI were detected by a triple quadrupole mass spectrometer. RESULTS Sampling of the specimens at the liquid bridge and ESI of the dissolved solutions both occurred around the probe apex. The sampling and ionization co‐existed in contact‐mode, while they were explicitly separated in the tapping‐mode. The one‐dimensional mapping of solid samples such as protein films and tissue sections was demonstrated. The results indicated that there was little cross‐contamination during the operation. CONCLUSIONS The method, named scanning probe electrospray ionization (SPESI), promises to be a simple and unique approach toward direct sampling and ionization methodology. Copyright © 2012 John Wiley & Sons, Ltd.