Micronutrient deficiencies include shortages of vitamins and minerals. They affect billions of people and are associated with long-range effects on health, learning ability, and huge economic losses. Biofortification of multiple micronutrients can play an important role in combating malnutrition. The challenge, however, is to balance plant growth with nutrient requirements for humans. Here, we summarize the major progress about vitamin biosynthesis and its response to the changing environment. We discuss the interactions among vitamins as well as possible strategies for vitamin biofortification. Finally, we propose to integrate new breeding technologies with metabolic pathway modification to facilitate the biofortification of crops, thereby alleviating the hidden hunger of target populations.