With Atleti having failed to convert their opening two penalties, Madrid captain Ramos proved their nemesis again when he sent Jan Oblak the wrong way.
Federico Valverde and Alvaro Morata - against his former club - spurned the best opportunities of a dour 90 minutes on Sunday, though the quality did improve in extra-time.
However, a string of excellent saves from both goalkeepers, either side of Valverde's late red card, forced penalties, with Saul Niguez and Thomas Partey missing from the spot.
The captain seals it for Real Madrid 🏆 pic.twitter.com/J6cBci0kL6— ESPN FC (@ESPNFC) January 12, 2020
Ramos kept his composure to take the title back to Santiago Bernabeu after Dani Carvajal, Rodrygo and Luka Modric also hit the target from 12 yards.