With the highest incidence, breast cancer is the leading cause of cancer deaths among women in the world. Tumor metastasis is the major contributor of high mortality in breast cancer, and the existence of cancer stem cells (CSCs) has been proven to be the cause of tumor metastasis. CSCs are a small proportion of tumor cells, and they are associated with self-renewal and tumorigenic potential. Given the significance of CSCs in tumor initiation, expansion, relapse, resistance, and metastasis, studies should investigate and discover effective anticancer agents that can not only inhibit the proliferation of differentiated tumor cells but also reduce the tumorigenic capability of CSCs. Thus, new therapies must be discovered to treat and prevent this severely hazardous disease of human beings. The success of platinum complexes in cancer treatment has laid the basic foundation for the utilization of metal complexes in the treatment of malignant cancers, in particular the highly aggressive triple-negative breast cancer. Importantly, metal complexes currently have diverse and versatile competences in the therapeutic targeting of CSCs. The anti-CSC properties provide a strong impetus for the development of novel metal-based compounds for the targeting of CSCs and treatment of chemotherapy-resistant and relapsed tumors. In this review, we provide the latest advances in metal complexes including platinum, ruthenium, osmium, iridium, manganese, cobalt, nickel, copper, zinc, palladium, and tin complexes against breast CSCs obtained over the past decade, with pertinent literature including those published until 2021.