Hand-to-Hand Combatant

Hand-to-hand fight - application of rough physical force with use of special receptions of fight, shock equipment.

Master Hand To Hand Combatant

 * Michael - he displays immense prowess in hand-to-hand combat, as he was able to easily block most of Lucifer blows and beat him to submission in seconds. He also effortlessly defeated Castiel armed with an angel blade before he could even attempt to stab him and instantly overpowered Sam before he could draw his gun and easily disarmed Dean of his Angel Blade and defeated him swiftly.
 * Cain - being the Father of Murder and the trainer of the Knights of Hell, Cain was a highly skilled martial artist. He was able to overpower and slaughter a battalion of demons with little effort. He was able to casually fight Dean when most of his powers were suppressed and retain the upper hand.
 * Gunner Lawless - easily defeated Dean Winchester

Expert Hand-to-Hand Combatant

 * Lucifer  - is a very accomplished fighter, with millenia worth of fighting experience. He was able to casually fight and overwhelm Dean, Sam, and Castiel (who he managed to also disarm) all at once, even while in his cage.He later effortlessly disarmed Dean of his gun and swiftly beat him to a bloody pulp in their altercation.Even while weakened due to his Grace depletion, Lucifer was still able to fight Castiel and force him to flee, although he got wounded in the process. In their final battle, despite Dean's power boost from Michael who Dean was acting as a vessel to, Lucifer was able eventually beat Dean in hand-to-hand combat, albeit aided by the fact that his strength was increased in his super-charged state and Lucifer's far greater experience in hand-to-hand combat.
 * Dean Winchester - he is adept with martial arts, and knife fighting as well; he has subdued several human assailants with ease in multiple episodes and bested physically more powerful creatures, often unarmed or equipped with only a blade. Dean has also beaten his younger brother Sam in a fight a few times. Due to his year-long stay in Purgatory and the realm's animal-like survival of the fittest environment, Dean greatly honed his hunting skills and instincts. Even when up against three demons, Dean was able to take them down single-handedly using only his hand-to-hand experience and the demon killing knife, something which impressed the powerful demon, and his ancestor, Cain greatly.
 * Castiel – he is an excellent hand to hand combatant. This skill has only improved over the course of the series, partly due to his time spent with the Winchesters who are formidable combatants themselves and his brief time spent as a Hunter-in-training. His skills show in his fights against other inhuman beings, as he is able to disarm many beings with Angelic weaponry and then use that weapon to kill them. He has proven capable of fighting his lesser angelic brethren with ease. This skill remained with him as he became a fallen Seraph or even human, as he managed to kill an angel in a broken bus without his powers, although the angel was caught off guard at the discovery that Castiel was now human. Castiel even held off two Leviathans with only his fists.
 * Ramiel - due to his millennia of experience, Ramiel was an expert hand-to-hand combatant capable of fighting three experienced hunters and a Seraph with great ease.

Skilled Fighter

 * Gordon Walker - was a very proficient combatant, capable of matching both Sam and Dean in a fight.