In order to expand the scope of volatile organic compounds (VOCs) in primary and secondary school textbooks, headspace-gas chromatography-mass spectrometry was used to detect the residual content of 25 kinds of volatile organic compounds. The experimental results show that the method has good separation effect, the recovery rate of 25 VOCs is good, and the relative standard deviation is less than 15%. The pretreatment was simple and the detection time of single sample was less than 1 h. Compared with the existing VOCs detection methods for primary and secondary school textbooks, more VOCs as much as 9 were detected, which provided the possibility of short-term and more comprehensive detection for centralized batch printed textbooks, and provided strong support for the quality control of primary and secondary school textbooks.