Early career Francisco Barrio started his
mixed martial arts career while training at
Nova União and the Pana Wrestling Team in Buenos Aires. His debut was in the lightweight division, on 14 July 2012, at Real Combat Conviction. He won via submission, with a rear-naked choke just 1:14 into the first round. On October 20, 2012 Francisco win Alexander Ceballos via Submission (keylock). At KIF 2 - Killer Instinct Fight 2, Croata defeated Esteban Zuñiga via TKO in first round.
FFC On June 27, 2013, Croata signed with the European MMA promotion,
Final Fight Championship. Francisco next defeated Patrick Peresa, after 54 seconds of the third round, by submission (Rear-Naked Choke) at FFC13. The official public page of
Final Fight Championship announced that Francisco will fight Vaso Bakočević in FFC on October 31, 2014, in a featherweight title eliminator. The fight failed to materialize, and Barrio was rescheduled to fight Filip Pejić at FFC 15. Pejić won the fight by a first-round knockout. After his loss to Pejić, Barrio took a five year break from the sport. He returned in December 2019, when he was scheduled to fight Adi Duraković at FNC 2. The fight ended after 18 seconds, as Duraković collapsed to the floor. Barrio fought again at FNC 3, against Aleksandar Janković. He beat Janković by a third-round submission via neck crank.
KSW Barrio signed with
KSW on October 31, 2020 and faced
Mateusz Legierski at
KSW 56: Polska vs. Chorwacja on November 14, 2020. He lost the fight via majority decision. His second fight with KSW came at
KSW 58: Kołecki vs. Zawada, when he faced Bartłomiej Kopera. Barrio won the fight by unanimous decision. Barrio was scheduled to face Vaso Bakočević at FNC: Armagedon Quarterfinals on September 11, 2021. He won the fight by a first-round submission. Barrio stepped in as a short notice opponent for Łukasz Rajewski at
KSW 70: Pudzianowski vs. Materla on May 28, 2022. He won the bout via rear-naked choke in the second round. Barrio faced Maciej Kazieczko at
KSW 76: Parnasse vs. Rajewski on November 12, 2022. He lost the fight by a third-round knockout. Barrio stepped in as a short notice opponent for Aymard Guih at
XTB KSW 93: Parnasse vs Mircea on April 6, 2024 in Paris and lost by Split Decision. ==Personal life==