With the application of genetic and molecular biology techniques, there has been substantial progress in understanding how vitamins are transferred across the mammalian blood–brain barrier and choroid plexus into brain and CSF and how vitamin homeostasis in brain is achieved. In most cases (with the exception of the sodium‐dependent multivitamin transporter for biotin, pantothenic acid, and lipoic acid), the vitamins are transported by separate carriers through the blood–brain barrier or choroid plexus. Then the vitamins are accumulated by brain cells by separate, specialized systems. This review focuses on six vitamins (B₁, B₃, B₆, pantothenic acid, biotin, and E) and the newer genetic information including relevant ‘knockdown’ or ‘knockout’ models in mice and humans. The overall objective is to integrate this newer information with previous physiological and biochemical observations to achieve a better understanding of vitamin transport and homeostasis in brain. This is especially important in view of the newly described non‐cofactor vitamin roles in brain (e.g. of B₁, B₃, B₆, and E) and the potential roles of vitamins in the therapy of brain disorders.