The Molotow is internationally acknowledged and has established a reputation^[7] for showcasing new talent and hosting many well-known bands' first shows at the beginning of their careers such as The Killers,^[8] The White Stripes,^[9][10][11] The Black Keys^[12] or Mumford & Sons^[13][14] and is noted for being a stepping stone for bands before they get famous. Others who have played gigs at Molotow early in their careers include Vampire Weekend,^[15][16] Biffy Clyro,^[17] Idles,^[18] The Hives, LCD Soundsystem,^[19] St. Vincent,^[20] The National^[21] and Imagine Dragons.^[22] Vice magazine wrote: 'Without the Molotow Rock'n'Roll in Hamburg would be lost long ago."^[23]

The Molotow was a hot spot for a 90s German indie rock movement going by the name of "Hamburger Schule". One of those bands, "Muff Potter", recorded a tribute song about the club entitled “Wir sitzen so vorm Molotow”^[24][25] which means "We're just hanging in front of the Molotow".

Hellacopters frontman Nicke Andersson said in 2005 when asked why he played at a small location like Molotow: "Rock 'n' roll is not made to be viewed with binoculars from a great distance, or on large screens".^[26]

In 2013 the building where the club was located got demolished and the Molotow moved to the other end of the Reeperbahn to Nobistor, next to the Beatles-Platz.^[27]

In 2016 a book about the Molotow by Sebastian Meissner was published by Junius Verlag.^{[28][29][30][31]}

During the COVID-19 pandemic in 2020 Frank Turner played an exclusive online stream show to help the Molotow during the crisis.^[32]

In December 2023, the Molotow received notice of termination from the location's tenant and was ordered to vacate it by 30 June 2024 at the latest.^[33] There was a solidarity demonstration, also covered by nationwide #1 evening news show Tagesschau, to support the Molotow on December 30th 2023 with several thousand people in front of the club.^[34][35] Ultimately, a temporary extension of the lease until December 31, 2024 was negotiated with the support of Hamburg's senator for culture and media, and the borough Hamburg Mitte.^[36]

In March 2025 the club moved to the old Top Ten Club location. The building was leased until at least 2037 by Hamburg Kreativ Gesellschaft, a public agency promoting creative industries in the city of Hamburg, and appropriate rooms were sublet to the Molotow.^[37]