Green tea extract epigallocatechin-3-gallate (EGCG), as a kind of natural active compounds, has become a research hotspot in cancer treatment. However, poor stability, low bioavailability and antitumor efficacy limit the application of EGCG. In this study, mesoporous dopamine (MPDA) with high drug loading and good biocompatibility loaded EGCG, garlic extract diallyl trisulfide (DATS) and photosensitizer (indocyanine green, ICG) by π-π stacking and hydrophobic-hydrophobic interaction, and the nano-system involved filling the mesoporous of the MPDA with phase change material (1-tetradecanol, 1-TD) molecules, which acted as a thermosensitive gatekeeper. The results indicated that MPDA-ICG@TD has an excellent photothermal effect and good stability. Due to the solid–liquid phase transition characteristics of the phase change material, MPDA-ICG@TD could control the release of drugs under near-infrared laser irradiation. Besides, cytotoxicity and apoptosis experiments showed that MPDA-ICG/EGCG/DATS@TD could be efficiently inhibited 4T1 cell proliferation and accelerate cell apoptosis than use diallyl trisulfide or EGCG alone, which means that the combination of natural active compounds EGCG and diallyl trisulfide has excellent synergy and can effectively improve the antitumor effect of EGCG. Moreover, this nano-system exhibited non-toxicity and good blood compatibility. This study provides a promising and effective strategy for improving the antitumor efficacy of natural active compound EGCG.