At the age of 16, she married Neal Cassady who took him on the road and made him meet the writer Jack Kerouac. The latter becomes their travel companion and retranscribes their adventures in the novel On the Road where LuAnne appears under the name of Marylou. Charmed by the young woman, Kerouac calls her "Golden Beauty", creating a love triangle between the three friends.

LuAnne and Neal divorced in 1948, after fifteen months of union. They remain close despite the remarriage of Neal with Carolyn Robinson in 1949.