This chapter deals with B-vitamins, which is involved in various physiological processes of plants, viz. participation in nutrient uptake, seed germination, vegetative growth, crop productivity in the improvement of vegetables, cereals, leguminous, aromatic oil crop, and particularly sugarcane crop. However, our understanding of the mode of B-vitamin action in plant is lagging far behind the level of understanding of the phytohormone action. The role of vitamins in some areas of plant physiology including vernalization, photoperiodism, phytohormone action, biological nitrogen fixation, and enzymatic action has still not been studied completely so far. The possibility of commercial exploitation of vitamins in agricultural domain particularly vitamin B6 (pyridoxine) in sugarcane crop improvement has also been discussed with soil applied rice bran and seed-sett pyridoxine soaking with improved cane yield and quality.