Abstract: The quality and safety of children’s textiles, especially chemical safety, is very important. The harm to children caused by using unsafe products is immeasurable. At present, the chemical safety research of textiles usually focuses on the specific target substances specified in the regulations. The detection methods are mainly to detect the content of target substances in the sample to determine whether it meets the regulatory requirements. In fact, although the known chemicals in the product meet the regulatory requirements, other unknown chemicals may exist potential hazards to children’s health. Therefore, it is necessary to screen potential chemicals in children’s textiles by non-targeted method in order to more comprehensively screen the chemical risks in product. Non-targeted analysis of potential chemical substances in imported children’s textiles using gas chromatography-Orbitrap high-resolution mass spectrometry (GC-Orbitrap MS) was established. Unknown substances were qualitatively assessed by using the comprehensive score and retention index, identifying the molecular formula by chemical ionization, comparing fragment ion data to distinguish isomers, and verifying according to chemical standards. A total of 48 substances were identified in 40 children’s textiles, including 21 esters, 8 ketones, 6 amines, 4 ethers, 3 alcohols, 3 phenols and 3 other substances. The identified substances were statistically and semi-quantitatively analyzed. Dibutyl phthalate, tolylene-2,4-diisocyanate, isopropyl palmitate and 1,2,4-butanetriol were identified in the imported children’s textiles, and their detection rates were greater than or equal to 10%. The identified substances were further filtered and screened according to detection rates, toxicities and response intensities. Then the high-risk chemicals in the children’s textiles were found. This method can provide a new way for screening potential chemicals in textiles and other products, and play a positive role in carrying out product chemical risk monitoring and promoting product quality and safety.