High global incidence of prostate cancer has led to a focus on prevention and treatment strategies to reduce the impact of this disease in public health. Boron compounds are increasingly recognized as preventative and chemotherapeutic agents. However, systemic administration of soluble boron compounds is hampered by their short half-life and low effectiveness. Here we report on hollow boron nitride (BN) spheres with controlled crystallinity and boron release that decrease cell viability and increase prostate cancer cell apoptosis. In vivo experiments on subcutaneous tumour mouse models treated with BN spheres demonstrated significant suppression of tumour growth. An orthotopic tumour growth model was also utilized and further confirmed the in vivo anti-cancer efficacy of BN spheres. Moreover, the administration of hollow BN spheres with paclitaxel leads to synergetic effects in the suppression of tumour growth. The work demonstrates that hollow BN spheres may function as a new agent for prostate cancer treatment.