Abstract: Boron Neutron Capture Therapy (BNCT) is a binary targeted radiotherapy technique that combines biological and physical targeting. Its core principle lies in the delivery of boron-10 (¹⁰B) to tumor sites via tumor-specific carriers, followed by thermal neutron irradiation. This triggers the ¹⁰B(n,α)⁷Li nuclear reaction, generating high linear energy transfer particles (alpha particles and ⁷Li ions) that precisely destroy cancer cells. With advancements in key facilities such as neutron sources, significant progress has been made in the innovative design and clinical translation of boron-containing drugs, which are central to BNCT efficacy. This article systematically reviews the evolution of three generations of boron carriers, from nontargeted small molecules to intelligent delivery systems. It focuses on analyzing the molecular design strategies and targeting advantages of third-generation agents—including targeted amino acid/sugar derivatives, nanocarriers, and antibody-drug conjugates—and summarizes key outcomes from global BNCT clinical trials. Although challenges remain, such as precise monitoring of intratumoral boron concentration and the establishment of standardized treatment protocols, BNCT demonstrates considerable potential as a promising modality for treating refractory solid tumors through continued interdisciplinary collaboration.