2D phosphorene, arsenene, antimonene, and bismuthene, as a fast‐growing family of 2D monoelemental materials, have attracted enormous interest in the scientific community owing to their intriguing structures and extraordinary electronic properties. Tuning the monoelemental crystals into bielemental ones between group‐VA elements is able to preserve their advantages of unique structures, modulate their properties, and further expand their multifunctional applications. Herein, a review of the historical work is provided for both theoretical predictions and experimental advances of 2D V‐V binary materials. Their various intriguing electronic properties are discussed, including band structure, carrier mobility, Rashba effect, and topological state. An emphasis is also given to their progress in fabricated approaches and potential applications. Finally, a detailed presentation on the opportunities and challenges in the future development of 2D V‐V binary materials is given. 2D V‐V binary materials, as the internal combination of group‐VA elements (N, P, As, Sb, Bi), have become a popular research topic. Through the interaction among charge, orbital, lattice, and spin degrees of freedom, the favorable and superior properties in 2D V‐V binary materials can be further modulated, extending their application in novel electronic, optoelectronic, and energy devices.