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Navy was a dark shade of blue used in clothing. (PROSE: Exodus Code)
The Eighth Doctor occasionally wore a navy frockcoat. (COMIC: Dreadnought) He also wore a navy leather peacoat. (AUDIO: Dark Eyes, Stranded, Day of the Master)
The First Doctor wore a navy ribbon tie, (TV: An Unearthly Child, etc) most notably when he first met Daleks during the Dead Planet Incident, (TV: The Daleks)
The Twelfth Doctor wore a navy crombie coat. (TV: Deep Breath, etc.) He also wore a navy top hat during his visit to the 1814 frost fair. (TV: Thin Ice)
The Tenth Doctor wore a tie with a deep navy blue background and a crimson flora random design. (TV: Daleks in Manhattan/Evolution of the Daleks) He later wore a navy blue tie with burgundy circles in a diagonal grid. (TV: The Impossible Planet)
The Eleventh Doctor wore a navy bow tie when he witnessed the birth of the New Dalek Paradigm during the Ironside Incident. (TV: Victory of the Daleks)
The Third Doctor wore a smoking jacket of navy velvet with a rolled collar when he first met the Silurians. (TV: Doctor Who and the Silurians)
The Seventh Doctor wore one navy blue sock. (PROSE: Return of the Living Dad)
Sarah Jane Smith wore a navy top during her 'final' farewell with the Tenth Doctor. (TV: School Reunion)
Maria Jackson sometimes wore navy denim jackets. (TV: Eye of the Gorgon, The Warriors of Kudlak, Whatever Happened to Sarah Jane?, The Last Sontaran)
Clara Oswin, the Victorian incarnation of Clara Oswald, wore a navy bustle dress. (TV: The Snowmen)
Martha Jones wore a navy jumper with a v-neck collar, as did her clone when posing as her during the 2009 Sontaran invasion of Earth. (TV: The Sontaran Stratagem|The Poison Sky)
Yasmin Khan wore a navy walking suit with a white blouse during her encounter with Nikola Tesla. (TV: Nikola Tesla's Night of Terror)
Ace wore a white blouse with navy stripes. (TV: Remembrance of the Daleks, The Happiness Patrol, The Greatest Show in the Galaxy)
On her visit to Messaline, Donna Noble wore a navy blouse with buttons. (TV: The Poison Sky, The Doctor's Daughter)
The Sixth Doctor wore a navy waistcoat when he and Evelyn Smythe met Cybermen on Chronos during 3286. (WC: Real Time)
The Ninth Doctor wore a navy jumper when he and Rose Tyler met Charles Dickens and the Gelth. (TV: The Unquiet Dead)
Toshiko Sato wore a navy pencil skirt. (TV: Out of Time)
Sally Sparrow wore a navy sweater-vest when she met Weeping Angels. (TV: Blink)
A parallel version of the Doctor wore a navy jumper. (AUDIO: The Emporium At The End)
The Master's Tremas incarnation wore a navy shirt with a white collar when he met the Seventh Doctor, Ace and the Cheetah People. (TV: Survival) He also wore a single-breasted waistcoat of navy moleskin with orange plaid symbols during his spy incarnation. (TV: Spyfall, Ascension of the Cybermen|The Timeless Children)
Many Sontarans wore navy blue helmets and pauldrons on their space armour. (TV: The Sontaran Stratagem|The Poison Sky, The Last Sontaran, The End of Time, The Pandorica Opens, A Good Man Goes to War, The Crimson Horror; AUDIO: The Sontaran Ordeal, The Eternity Cage, The Great Sontaran War, The Sontaran Project; COMIC: Fugitive, The Instruments of War, Supremacy of the Cybermen)
The Dream Lord wore a navy tie when he mentions about the consequences of the Eleventh Doctor, Amy Pond and Rory Williams dying on the dream and the real world. (TV: Amy's Choice)
Doctor Olivia Steele wore a navy pencil skirt. (PROSE: Exodus Code)