This chapter describes benefits of biodegradable base stocks and attempts to bring out the greener advances made in synthesis methodologies for the industrial applications of electrical transformer oils, refrigeration oils, metal-working coolants, food-grade lubricants, vegetable oils (VO)-derived diesel lubricity improvers, and VO-based greases. Typically, VO and synthetic ester-based lubricants offer excellent features with respect to high-viscosity index, high flash point, and high degree of biodegradability. Lubricants are complex products consisting of 70%–99% base oils admixed with additives that modify the natural properties of the fluid to meet its intended requirements. Owing to the global environmental imbalance, there are some critical issues related to the area of lubrication, as large quantities of petroleum or mineral oil-based industrial lubricants on disposal or break down are a potential threat to the environment. Polyol esters are a class of synthetic lubricants which are derived from fatty acid and polyols.