Disclosed is the crystalline form F of zofenopril calcium having the characteristic XRPD peaks as described herein. Also disclosed is a process for the production of crystalline form F of zofenopril calcium comprising (a) dissolving an amine salt of zofenopril in a water miscible organic solvent which is free of added water (b) mixing the solution obtained in step (a) with an aqueous solution of a calcium salt and (c) isolating the zofenopril calcium form F. The use of zofenopril calcium of form F in the manufacture of a medicament for the treatment of hypertension, cardiac decompensation, myocardial infarction, acute myocardial infarction, heart failure or chronic heart failure is also disclosed.
