The present invention relates to a novel anhydrous crystalline form of zofenopril calcium of formula (I), chemically known as (4S)-1-[(2S)-3-(benzoylthio)-2-methylpropionyl]-4-(phenylthio)-L-proline calcium salt or hemi-calcium salt. The present invention further relates to a process for the preparation of the new crystalline form of zofenopril calcium, its use in pharmaceutical compositions and the use of the new crystalline form and compositions in the treatment of hypertension and various other diseases.