C.sub.3-12 alkyl, substituted alkyl, alkenyl and cycloalkyl cyanoacetates are prepared by an efficient and simplified one-step process in which a small molar excess of the corresponding alcohol, i.e., C.sub.3-12 alkyl, substituted alkyl, alkenyl or cycloalkenyl alcohol is reacted with crystalline cyanoacetic acid, or a concentrated aqueous solution of cyanoacetic acid, in the presence of an acid catalyst, such as, for example, methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid and phosphoric acid at a temperature in the range of from about 60.degree. C. to about 150.degree. C., in accordance with the following reaction: CNCH.sub.2 COOH+R--OH.fwdarw..sup.(cat) CNCH.sub.2 COOR+H.sub.2 O (I) where R is a C.sub.3-12 alkyl, substituted alkyl, alkenyl or cycloalkyl.