CQC is a complicated thing. It's not as easy as A>B>C>D, mainly because CQC is divided into two different categories: armed and unarmed.
Going strictly by showings, Liquid is the best as armed CQC. Old Snake's CQC fight in Big Mama's place is far more impressive than Naked Snake's fight against the Ocelot unit, and Liquid pwned Snake in armed CQC. So, for armed, it's gotta be Liquid>Solid>Naked. I'm not including The Boss because she's never gotten into any armed fights.
Unarmed, The Boss>Naked>Solid>Liquid. The Boss owned Naked in H2H combat, who got Snake into a CQC hug, who beat Liquid both in MGS1 and 4.
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