A biological sample can be subjected to measurement, description and ionization of ions is possible under atmospheric pressure without undergoing pretreatment. Imaging having a resolution on the nanometer order can be performed. An STM needle (probe) of an XYZ-axis-drive piezoelectric element is oscillated along the Z axis to contact the sample to a depth on the nanometer order and capture molecules at the needle tip. A pulsed high voltage is applied to the needle, achieving needle electrospray. The sample molecules are then desorbed and ionized, and mass spectrometry is carried out. The needle is swept in the XY directions, oscillation is repeated and an image obtained by molecular imaging of a nanometer area of the biological sample is measured. The probe may be brought into contact with a droplet produced at the tip of a capillary connected to the outlet port of a liquid chromatograph to capture a sample.