Flavour additives with carboxyl and hydroxyl groups (FACHs), the key ingredients in characteristic flavours, are frequently detected in cigarette smoke. They are attracting increasing attention in regulating the flavour additives used in tobacco to curb youth tobacco use and prevent the use of additives that are harmful. In this study, a highly robust, sensitive, and precise method based on silylation and GC-MS/MS with an improved backflushing system was developed for the simultaneous analysis of 171 FACHs in cigarette smoke. Silylation has been shown to have advantages in terms of high selectivity and sensitivity to chemicals with carboxyl and hydroxyl groups, especially when combined with GC-MS/MS. The extraction and silylation conditions were optimised. Dichloromethane was used as the extraction agent. BSTFA in combination with 1% TMCS and 0.2% TMSI was selected as silylating agent for high silylation efficiency, particularly for hindered analytes. The method has been validated. The limit of detection (LOD) ranged from 0.6 to 332.3 ng/mL. 91.1% out of the analytes in QC samples had precisions lower than 10% during one month run. The improved backflushing system with a fused silica splitter was shown to be crucial in the excellent long-term robustness of the method. The developed method was used to determine flavour additives in 270 practical cigarette smoke samples with reliable results. A total of 154 FACHs were identified with wide-range levels among different cigarette brands.