Polyglycerol compositions comprise no more than about 5% by weight of monoglycerol based on non-water ingredients of the polyglycerol composition, and have a combined tetraglycerol and higher polyglycerol content of at least about 55%. Methods of making such compositions from a crude glycerin comprising from 0.01 to 5 wt % of glycerol-containing compounds comprising acetate ester moieties are described.