What episode does black organization appear in Detective Conan?

Answer 1

The first episode they appear in is episode 1, in which two members clad in black (later found out to have the code names Gin and Vodka), shrink Shinichi. After episode 1, they, along with members Vermouth, Chianti, Korn, Calvados, Sherry (Haibara), Pisco, Tequilla, Kir (Hidemi Hondou), Akemi, and others appear in:

128 The Black Organization 1 Billion Yen Robbery Case

129 The Girl from the Black Organization and the University Professor Murder Case

176 Meeting With the Black Organization Again (Haibara)

177 Meeting With the Black Organization Again (Conan)

178 Meeting With the Black Organization Again (Resolution)

309 Contact With the Black Organization: Negotiation Chapter

310 Contact With the Black Organization: Pursuit Chapter

311 Contact With the Black Organization: Desperation Chapter

345 part 1 Head-to-Head Match With the Black Organization; Two Mysteries of the Night of the Full Moon

345 part 2 Head-to-Head Match With the Black Organization; Two Mysteries of the Night of the Full Moon

425 Black Impact! The Moment the Black Organization Reaches Out!

462 Shadow of the Black Organization: The Young Witness

463 Shadow of the Black Organization: The Strange Illumination

464 Shadow of the Black Organization: The Mystery of the Big Reward

465 Shadow of the Black Organization: The Pearl Shining Star

491-504 Clash of Red and Black

Also, they have been in 2 movies; movie 5 (countdown to heaven) and movie 13 (the raven chaser)