Golino was born in Naples, Italy, the daughter of an Italian father who was a Germanist scholar, and a Greek mother, Lalla, who was a painter. One of her grandmothers was Egyptian-French. She grew up in an "artistic household" and, after her parents split up, was raised alternating between Athens and Sorrento (Naples). Golino is the niece of the journalist Enzo Golino at L'Espresso, and her brother is a musician. When she was a girl, her mother frequently took her to the cinema houses, and she quickly became interested in films. But in spite of this, she never thought about pursuing a film career until she made her first movie. Instead, she wanted to be a cardiologist. Valeria was diagnosed with scoliosis at age 11, and she had to have a steel rod implanted in her back for five years. She remained in the care of a surgeon in Chicago for six months, where she learned to speak English. At age 14 she started to work as a model in Athens, Milan, London, and Los Angeles. She was in TV commercials for beer, perfume, and cosmetic, and she modeled swimsuits and blue jeans. Being an unfocused student, she dropped out of high school after acting in her first movie.