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9-Nitro-20(S)-camptothecin (9-NC) is a broad-spectrum anticancer drug but its application was limited by its poor solubility in aqueous medium. Novel polymeric micelles were developed for 9-NC delivery. The micelles were fabricated from the self-assembly of amphiphiles with cinnamic acid (CIN) as lipohilic moiety and methoxy poly(ethylene glycol) (mPEG) as hydrophilic segment. The micelles were nontoxic to NIH 3T3 fibroblasts. 9-NC was trapped efficiently in mPEG–DCIN micelles. The release of 9-NC from the micelles with one cinnamic acid molecule as lipophilic moiety (mPEG–CIN) was much faster than that from the micelles with two cinnamic acid molecules as lipophilic moiety (mPEG–DCIN). The in vitro anticancer inhibition study demonstrated that the anticancer activity of 9-NC loaded mPEG–DCIN micelles was much better than that of 9-NC loaded mPEG–CIN micelles.