I think he already has the booking to CDG.

Personally, three different tickets with as many airlines is too many "moving parts" for comfort. If the CDG-MAD-LCG/SCQ flights in one single ticket (with Air France and Air Europa) are too expensive, and you have the Avios, you could book the 18.45 from ORY, which gets you in MAD in time for the late evening flights to Galicia, and change it if your flight is very delayed.