A series of l-[3-(acylthio)-3-aroylpropionyl]-~-proline derivatives was synthesized. A number of these compounds are potent angiotensin converting enzyme (ACE) inhibitors that lowered blood pressure in aorta-coarcted renal hypertensive rats. The most active derivatives are l-[3 (R)-(acetylthio)-3-substituted-benzoyl)-2 (S)-methyl-propionyll-prolines with an in vivo activity equivalent to SQ 14,225 (captopril). Structure-activity relationships are discussed. ...