Ronaldo received the top gong in recognition of his stellar campaign last season that saw him score 31 goals in just 30 matches for Real Madrid.
The Portugal captain also took out the Best Forward award and Best Goal for his incredible backheel against Valencia in May.
"I have to thank my team-mates, Real Madrid, my family... it is a very good moment in my career," Ronaldo said.
"For me, the important thing is to win collective prizes, but I like the individual ones, too. I work every day, in training, to continue adding more to this."
The 2013-14 Coach of the Year went to Argentine Diego Simeone after defying the odds to guide Atletico Madrid to the La Liga title last term.
Atletico remarkably topped the standings ahead of fancied duo Barcelona and Real for their first league crown since 1995-96.
"I want to share this with my players, without whom none of this would be possible," Simeone said afterwards.
"Thanks to Koke, Gabi, Miranda, [Thibaut] Courtois... and everyone who made it possible to win the title."
Costa Rica international Keylor Navas was named the Best Goalkeeper for his consistent season with Levante before making the switch to Real.
Real star Sergio Ramos took out the Best Defender, while team-mate Luka Modric (Best Defensive Midfielder) and Barcelona veteran Andres Iniesta (Best Attacking Midfielder) took out the respective midfield awards.
Granada's Yacine Brahimi received the Best African Player award, while Sevilla striker Carlos Bacca was named the best South American.
Revelation of the Year went to Barcelona youngster Rafinha Alcantara, who spent last season on loan at Celta Vigo.
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