Background: Camellia sinensis is an important economic crop with fluoride over-accumulation in the leaves, which pose a serious threaten to human health due to its leave being used for making tea. Recently, our study found that cell wall proteins (CWPs) probably play a vital role in fluoride accumulation/detoxification in C. sinensis. However, CWPs identification and characterization were lacking up to now in C. sinensis. Herein, we aimed at characterizing cell wall proteome of C. sinensis leaves, to develop more CWPs related to stress response. A strategy of combined cell wall proteome and N-glycoproteome were employed to investigate CWPs. CWPs were extracted by sequential salt buffers, while N-glycoproteins were enriched by hydrophilic interaction chromatography method using C. sinensis leaves as a material, afterwards all proteins were subjected to qualitative analysis via UPLC-MS/MS.Results: 501 and 195 CWPs were identified by cell wall proteomic and N-glycoproteomics profiling, respectively, with 118 CWPs being in common. Notably, N-glycoproteome is a feasible method for CWPs identification and consequently enhance CWP coverage. Among identified CWPs, proteins acting on cell wall polysaccharides constitute the largest functional group with most of them possibly being involved in the remodeling of cell wall structure. The second abundant group encompass mainly various proteases, being considered to be related to CWPs turnover and maturation. Oxidoreductases represent the third abundance with most of them especially Class III peroxidases being known to be implicated in defense response. As expected, identified CWPs emphasized on plant cell wall formation and defense response.Conclusion: This was the first large scale survey of CWPs by cell wall proteome and N-glycoproteome in C. sinensis. The results not only provides a database that will aid deep research on CWPs, but also improve the understanding underlying cell wall formation and defense response in this important economic specie.