Reduced calorie food compositions are prepared using fatty acid esterified alkoxylated polyol fat substitutes derived from C.sub.3 and higher epoxides and having a high proportion of primary ester linkages. The fat substitutes may be obtained by alkoxylation of a polyol such as glycerin with the epoxide in the presence of a cationic/ring-opening polymerization catalyst, followed by esterification with a fatty acid or a fatty acid equivalent.