I have found a picture and now I can confirm it. He is wearing both crosses, among others, including the Order of Isabel la Catolica.
You are right, it is Carlos III (which he had); but I am fairly sure the star is the Saint Esprit, although both are very similar with different centres.
The sash seems to be the order of Carlos III.
I Know it took place during the francoist regime, but were there any royals attending the late duke of Cádiz wedding to the caudillo's grand-daughter, apart from members of the spanish RF ?
The groom's father, the King of France and Navarre, was present for the wedding. He wore the collar, star, and sash of the Order of the Holy Spirit.
1364