Tobacco minor alkaloids are important precursor substances of TSNAs. Therefore, their accurate quantifications are of great significance. In order to realise determinations of seven minor alkaloids in mainstream cigarette smoke with high accuracy and robustness, the compensation effects of novel suitable analyte protectants (APs) for matrix effects were investigated. Through comparing the heights and shapes of chromatographic peaks before and after the additions of APs in standard solutions prepared in CH₂Cl₂ and cigarette smoke solution, the compensation effects of 12 APs and their combinations on the matrix effects of seven minor alkaloids were evaluated, and the best combination of 2-(pyridine-3-yl) ethan-1-amine (2 mg/mL) + 1,2-decanediol (1 mg/mL) was identified. This AP combination could effectively improve the shapes and increase the heights (by 7 % - 337 %) of chromatographic peaks for standard solutions prepared in CH₂Cl₂ and cigarette smoke solution. Before the addition of this AP combination, slope ratios of calibration curves for the two types of standard solutions of seven target chemicals were 71.4 % - 159.8 %, while after the addition, the slope ratios were 87.4 % - 105.6 %, indicating this AP combination reduced the matrix difference between pure solvent and cigarette smoke solution. After the addition of the AP combination, the standard curves of solutions prepared in CH₂Cl₂ showed good linearity (r² ≥ 0.999), the spiked recoveries were between 80.9 % - 119.6 %, and the inter- and intra-day precisions were between 1.5 % - 9.5 % and 3.1 % - 8.5 % respectively. Three commercial cigarette samples and one mixed standard solution were also tested under five different instrument working conditions to verify the intermediate precision of the method, and the results showed that the RSD values were higher (3.5 % - 25.4 %) without the AP combination and smaller (< 6.7 %) with the AP combination. Due to its high accuracy, precision, and robustness, this method has good application prospects.