On May 26, 2001 Bolocco married former Argentine ex-president Carlos Menem in La Rioja, Argentina, whom she met while interviewing him at the Casa Rosada presidential house in Argentina.They separated in April, 2007.
Bolocco was selected Miss Chile for Miss Universe on April 20, 1987. On May 26, 1987 she beat 67 contestants to become the first Chilean to win the Miss Universe beauty pageant.