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A novel amphiphilic chitosan, N,N-dilong chain alkyl chitosan (NCS), was applied to prepare self-assembled vesicles for DDS and NCS/PLLA blend for tissue engineering scaffold. The morphology of NCS self-assembled vesicles was investigated by SEM. Drug-releasing rates of vesicles made from longer alkyl chain and/or larger backbone molecular weight of NN-dialkyl chitosan are slower than shorter and smaller ones, and equilibrium drug-releasing ratios as well as releasing rates. The bio-experimental results indicate that NCS/PLLA blends are biodegradable and nontoxic. NCS is benefit to improve the cell affinity of PLLA.