Myers was born in Canterbury, Sydney, on 2 August 1930, to a violinist mother and marine wireless operator father. She displayed a talent for art at an early age. The family moved to Box Hill, Melbourne in 1941 and Vali left home at 14. After working in factories to support her dance lessons, she became immersed in dance and later became the leading dancer for the Melbourne Modern Ballet Company. In 1949 at age 19 Myers travelled to impoverished post-war Paris to pursue a dance career but found herself living on the streets of the Saint-Germain-des-Prés Quarter on the Left Bank. Love on the Left Bank is a 1954 book of photographs from Dutch photographer Ed van der Elsken (1925–1990), documenting the bohemian life on the Rive Gauche of Paris Vali Myers is the heroine of this semi-biographical roman à clef, and is also photographed along with some of her early drawings.
Myers was a flamboyant fantasy artist who worked in pen and ink and watercolour as well as being a nightclub dancer. She divided her life between her adopted home of Melbourne, the Hotel Chelsea in New York City, Paris, and a 14th-century cottage in a valley near Il Porto (Positano), Italy.
Her visionary art works developed from early detailed monochromes to a full range of vibrant colours and tones extending to watercolour and gold leaf, displaying a "fastidiously rendered depiction of a personal spirit world". She was acquainted with many celebrities and creatives including Tennessee Williams, Salvador Dalí, Django Reinhardt, Jean Cocteau, Patti Smith, Jean Genet, Sam Shepard and many others.
Myers paintings have sold for up to $US40,000 ($A68,000) in New York. Her work was held in the Stuyvesant collection in the Netherlands, New Yorks Hurryman Collection, and is owned by private collectors such as George Plimpton and Mick Jagger.