Edible phytosterol-containing compositions include molecular complexes of non-esterified phytosterols (P) and glycerine (G) in the form of liquid crystalline microparticles. Addition of an emulsifier (M) such as a monoglyceride or a modified lecithin, and optionally an ionic surfactant, to the complex facilitates its dispersal in an aqueous medium. A composition containing either the binary PG or ternary PGM molecular complexes can be formulated as a beverage, food product, or nutritional supplement. When administered to a human subject, the complexes sequester cholesterol in the gastrointestinal tract and reduce LDL cholesterol and total plasma cholesterol levels.