Abstract Cholesteryl esters of variously labelled fatty acids have been synthesized in high yield by 1,1′‐carbonyldiimidazole activation of the acyl group and reaction of the resulting acylimidazole derivative with cholesterol. The method has been used to synthesize cholesteryl esters on micro and semimicro scales. Syntheses of the following esters are reported: cholesteryl palmitate‐1‐ 14 C, cholesteryl palmitate‐d 31 , cholesteryl palmitate‐2,2‐d 2 , cholesteryl palmitate‐d 31 , cholesteryl palmitate‐2,2‐d 2 , cholesteryl palmitate‐3,3,4,4,5,5,6,6,7,7,8,8,9,9,‐10,10,11,11,12,12,13,13,14,14,15,15,16,16,16‐d 29 , cholesteryl 5‐doxylpalmitate and cholesteryl 16‐doxylstearate.