The invention provides an LC-Q-TOF/MS detection technique for 544 pesticide residues in solanaceous fruit vegetables. In a TOF/MS mode, LC-Q-TOF/MS measures the retention time of each pesticide standard substance under specified chromatographic and mass spectrometric conditions, an ionization form and a chemical formula of each compound under an ESI source are determined, the exact mass number for parent ions of each compound is obtained, and a TOF/MS database is formed. In a Q-TOF/MS mode, fragment ion mass spectra of each pesticide standard substance in 3-5 different collision energies are collected respectively, the collected information is introduced into PCDL software, and a Q-TOF/MS database is formed. Through comparison of the retention time and first-level mass spectrometry and second-level mass spectrometry information of solanaceous fruit vegetable samples, whether the samples contain the pesticide residues is determined, compounds having higher first-level score are subjected to second-level confirmation, and if the second-level score is higher, related pesticide residues are confirmed to be detected out. The method has the advantages of high speed, high throughput, high precision, high reliability and the like, and can accurately screen the pesticides in the solanaceous fruit vegetables.