The French striker, who is second behind Ronaldo in Los Blancos' all-time goalscoring charts, added another impressive three to his collection in the convincing win at the Bernabeu.
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After Rodrygo broke the deadlock on 22 minutes, Benzema doubled Real's advantage.
He headed home from close range after Vinicius Jr's cross from the left deceived the Real Valladolid defenders and goalkeeper Sergio Asenjo.
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Just three minutes later Benzema had his second and Real's third with a lovely curling effort into the top right-hand corner.
And four minutes after that the Ballon d'Or winner completed his hat-trick with a stunning overhead kick as he met Rodrygo's cross from the right.
Marco Asensio added a fifth on 73 minutes, while Lucas Vazquez made it 6-0 in stoppage-time to complete the rout.
But the win was all about Benzema, who is now level with Ronaldo for goals with Real Madrid boss Carlo Ancelotti with the pair both scoring 112 times under the Italian's guidance.
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However, the record goalscorer under Ancelotti is former AC Milan striker Filippo Inzaghi, who has 161 strikes to his name.
Real Madrid are second in LaLiga, 12 points behind runaway leaders Barcelona.