Covalent modification of shortened multiwalled carbon nanotubes (MWNTs) with a natural low molecular weight chitosan (LMCS) was accomplished by the nucleophilic substitution reaction. The LMCS modified MWNTs (MWNT-LMCS) were characterized by FTIR, solid-state 13C NMR, and XPS spectroscopies, thermogravimetric analysis, and transmission electron microscopy. The results revealed that amino and primary hydroxyl groups of the LMCS participated mainly in the formation of the MWNT-LMCS conjugates. The MWNT-LMCS consists of 58 wt.% LMCS, and about four molecular chains of the LMCS were attached to 1000 carbon atoms of the nanotube sidewalls. As a novel derivative of the MWNTs, the MWNT-LMCS not only solved in DMF, DMAc and DMSO, but also in aqueous acetic acid solution.