Herein, a novel molecule S4, which could form a uniform S4 spherical aggregate in water, was synthesized, and the S4 aggregate was used to load Dox to prepare the S4@Dox nanomedicine. The loading efficiency was 80.0 ± 4.5%. The pH response and slow release of Dox were the typical characteristics of the S4@Dox nanomedicine. In vitro experiments showed that cancer cells could successfully phagocytose S4 aggregates and the S4@Dox nanomedicine. The toxicity of S4 aggregates to MCF-7, HepG2, and H22 cells was low, and the S4@Dox nanomedicine had better antitumor activity and specific targeting, especially to the MCF-7 cells. The antitumor activity in vivo and in the tissue section showed that the S4@Dox nanomedicine could significantly reduce Dox toxicity, effectively induce the apoptosis of cancer cells, and effectively inhibit tumor growth, which showed that the nanomedicine had better antitumor activity.