Vivienne Acheampong worked as a supply teacher to help pay the bills between acting gigs. Acheampong has been acting for several years, appearing in bit parts as early as 2015. She was a voice actor in the World of Warcraft: Battle for Azeroth video game in 2018, but her big breakthrough moment came later that year when she made her first appearance in the BAFTA-nominated comedy sketch show Famalam. She would go on to appear in seven episodes from 2018 to 2020.
In 2020 she appeared on The Emily Atack Show. Later that year she starred as Alice's Mum in the Robert Zemeckis movie The Witches, an updated adaptation of the classic Roald Dahl story featuring Anne Hathaway, Octavia Spencer, Chris Rock and Stanley Tucci.
Acheampong appeared as Grace Kenu in the UK series The One in 2021, and in 2022 she starred in multiple episodes of Ellie & Natasia, as well as Lucienne in The Sandman on Netflix.