The content of total nicotine, free nicotine, bound nicotine and pH of total particulate matter (TPM) value of domestic tobacco from 38 representational brands were measured and the relationship between the nicotine forms and TPM pH of cigarettes smoke were investigated by simple correlation analysis and intrinsic relevance analysis. The results of the simple correlation analysis showed that the content of free nicotine was significantly positively correlated with TPM pH with a correlation coefficient of 0.846, the ratio of free nicotine to total nicotine showed a significantly positively correlation with TPM pH with a correlation coefficient of 0.784. The result of intrinsic relevance analysis showed that the content of total nicotine affect the TPM pH markedly (P=0.016).