A surface analyzing method comprising an ion generation step for generating multiply-charged ions of specific ion species and specific charge state; a deceleration step for decelerating the generated multiply-charged ions to a lower kinetic energy than an energy of threshold of sputtering of an objective material; an irradiation step for irradiating the decelerated multiply-charged ions on the surface of a sample; and an analysis step for analyzing particles or light emitted from the surface of said sample by the irradiation of said multiply-charged ions. Apparatus is provided for carrying out the method. Since the ions irradiated on the sample surface are multiply-charged ions having a lower kinetic energy than that of threshold of sputtering of materials constituting a sample, the irradiated ions interact merely with the top surface layer of the sample whereby analyzed information merely from the top surface layer of the sample can be obtained, and as a result, the kind of atoms of the top surface layer of the sample and the bonding state of said atoms can be analyzed with high sensitivity and high resolution.