We have developed a new mass spectrometry based on a time-of-flight mass spectrometer combined with an ion attachment ionization technique (IA-TOF). An alkali ion attachment scheme can ionize organic molecules without producing fragment ions. The adduct ions distributing over a wide mass range can be investigated with a high mass resolution by time-of-flight mass spectrometers. A tabletop IA-TOF system was developed and applied to typical specimens in a gas-phase as well as in a solid-phase as a performance test. We have succeeded in a fragment-free ionization and a mass analysis with a high mass resolution over a wide mass range. The IA-TOF realizes an accurate and versatile real-time analysis.