Abstract: In order to investigate whether the pH of total particulate matter (TPM) can represent the acid-base balance of mainstream cigarette smoke, and to analyze the correlations between the TPM pH and the chemical components of mainstream cigarette smoke, a method for determining the TPM pH was developed. The correlations between the releases of the routine chemical components, plus 30 main acidic components, 40 main alkaline components and ammonia in mainstream smoke and the TPM pH of cigarette samples made of different single grade tobacco leaves and commercial cigarette samples were analyzed. The influences of adding acidic and alkaline components to cigarettes on the TPM pH were investigated. The results showed that: 1) Adding 1% (mass fraction) sodium chloride to isopropanol aqueous solution increased the differences of detected values of TPM pH among different samples and reduced the relative standard deviation of the measurement values. 2) The correlations between the releases of routine components, the main acidic components, the main alkaline components and ammonia in mainstream smoke and the TPM pH could not be verified on the two types of cigarette samples. 3) The ratios of nicotine release to the total release of acidic components, the total release of carboxyl units or the total release of hydrogen ions in mainstream cigarette smoke significantly correlated to the TPM pH, which could be verified on the different cigarette samples of the two types. 4) The contributions of 2-furoic acid, formic acid, glycolic acid and lactic acid to the total release of hydrogen ions in mainstream cigarette smoke were relatively higher; compared with the other acidic components in the smoke, the effects of these four acidic components on the TPM pH were greater at the same adding mass. The influence of adding ammonia on the TPM pH was stronger than that of nicotine.