The traditional method for the identification of paper from different origins relies on microscopy to observe the fiber morphology, which requires professional experience. In this paper, pyrolysis-gas chromatography-mass spectrometry was utilized to analyze five types of traditional Chinese handmade papers, e.g., ramie paper, bamboo paper, bark fiber paper (mulberry paper and kozo paper), and Langdu paper. The results demonstrated that this method can be used to differentiate the four types of handmade papers. A high phenolic compound content was detected in bamboo paper; macromolecular triterpenoids, e.g., β – amyrin, α – amyrin, and stigmastan- 3,5-diene were found in mulberry paper and kozo paper; while those compounds were not found in ramie paper. In particular, a large quantity of phytosterol compounds were found for the first time in Langdu paper. This not only can be used to differentiate Langdu paper from others, but also it helps to explain why Langdu paper can resist insect and mildew activities. Results of the study can provide experimental reference for characterization of traditional handmade Chinese papers via pyrolysis-gas chromatography-mass spectrometry.