With more than a millienia of experience as a Shinigami warrior, Genryusai Yamamoto (Bleach) is a grandmaster of Zanjutsu and Hakuda.
Yoruichi Shihoin (Bleach) is one of the greatest Hakuda masters ever known in Soul Society.
Sosuke Aizen (Bleach) is a master warrior with tremendous skill in both Hakuda martial arts and Zanjutsu swordmanship.
Ichigo Kurosaki (Bleach) has astounding talent for Zanjutsu, he quickly developed his skills solely from battle instead of formal training and instruction.
Urahara Kisuke (Bleach) possess far greater talent in Zanjutsu and Hakuda than most Shinigami Captains, maintain master level of skill without any long term training.
Nomura Fudo (Busou Shoujo Machiavellianism) is an extraordinary martial art genius.
The Fight (Cardcaptor Sakura) is a master of martial arts.
Spike Spiegel (Cowboy Bebop)
Hailed as the World's strongest martial art master, Ichijou Aoi (Choujin Koukousei-tachi wa Isekai demo Yoyuu de Ikinuku you desu!) has tremendous talent in martial arts particularly her mastery of swordsmanship.
Both Son Goku and Krillin (Dragon Ball) are highly skill masters of the Kame-Sennin Ryu/Turtle School Style of martial arts.
Tien Shinhan (Dragon Ball)
Having learned from her father, the Ox King, Chi-Chi (Dragon Ball series) is a master martial artist of the Kame-Sennin Ryu/Turtle School Style.
With his prodigious talent and further honed through a lifetime of battles, Madara Uchiha (Naruto) is a Taijutsu master of the highest caliber.
Might Guy (Naruto) is the most powerful Taijutsu master in Shinobi history.
Neji Hyuga (Naruto) was extremely talented in his clan's Gentle Fist martial arts...
...having learned and mastered some of its most powerful techniques solely from observation.
Rock Lee (Naruto) has trained relentlessly to be a great Taijutsu master, capable of fighting the most skilled opponents using pure Raw Power and skill.
Sakura Haruno (Naruto)
Originally watching his brother trained, Toki (Fist of the North Star) demonstrated his own fighting ability by brutally beating a hunter who had killed his pet dog.
Hayato Furinji (History's Strongest Disciple Kenichi) a well known user of this ability.
A master martial artist, Zeff (One Piece) is the founder of the Black Leg Style Martial Art which combines Brazilian Capoeira, French Savate and Korean Taekwondo.
Rob Lucci (One Piece) is a prodigious genius in the Rokushiki/Six Powers martial arts.
Ikki Kurogane (Rakudai Kishi no Cavalry) is a martial art master who invented Blade Steal, a skill that copies his opponents martial arts techniques and adapt it into his swordsmanship...
...derived from his Perfect Vision that allows him to grasp his opponents' movements and predict their movements, personality, and thoughts.
Rachel Moore (Case Closed)
Shinnosuke Nohara (Crayon Shin-chan: Burst Serving! Kung Fu Boys ~Ramen Rebellion~ ) has extraordinary talent for martial arts.
Vampires such as Angel (Buffy the Vampire Slayer) are naturally skilled at combat even upon being sired, able to fight with great skill and shoot with great accuracy even if they didn't have such skills as a human.
While she had poor fighting skills during her first year as a vampire, Harmony Kendall (Buffy the Vampire Slayer) began honing her instincts, allowing her to hold her own in combat.
The Third Doctor (Doctor Who) was skilled at martial arts, particularly Venusian aikido as demonstrated here.
Stick (Marvel Cinematic Universe) is immensely skilled martial artist even at the age of 90.