The 50-year-old, who led Newell's Old Boys to the Argentinian Clausura title last season but recently severed ties with the club, has agreed a two-year contract at Barca where he will replace Tito Vilanova.
"FC Barcelona have reached an agreement to appoint Gerardo Martino as the new coach of the football team for the next two seasons . This agreement is pending the drafting and signing of the contract," a statement on fcbarcelona.cat read.
"In the coming hours [a programme will be planned for] his arrival in Barcelona, signing the contract and the subsequent presentation."
A host of coaches were linked to the vacant position with the Spanish champions, including Luis Enrique, Andre Villas-Boas, Marcelo Bielsa, Michael Laudrup and Guus Hiddink, who yesterday resigned as coach of Anzhi Makhachkala.
However, Martino emerged as the favourite over the weekend and the former Argentina midfielder has been confirmed as Barca's new boss.
Martino had been in charge of Newell's in his native Rosario for the last two seasons, having previously also represented the club in three different spells as a player.
He also played for Spanish side Tenerife as well as Lanus in his homeland, Barcelona SC in Ecuador and O'Higgins in Chile.
Prior to taking over at Newell's, Martino spent four years as coach of Paraguay, from 2007 to 2011.
He led them to the quarter-final of the 2010 World Cup - the nation's best-ever performance in the competition - before losing 1-0 to eventual champions Spain.
The following year, Martino guided Paraguay to their first Copa America final since 1979 but were beaten 3-0 by Uruguay. He stepped down from his post later that month.
The news of Martino's impending appointment is sure to go down well with Barcelona talisman Lionel Messi, who has spoken in glowing terms about his compatriot in the past.
The two men both hail from Rosario and many in the media see the appointment as deliberate move from the Barcelona board to keep the four-time Ballon d'Or winner happy.
Speaking a year ago, Messi told Diario Ole: "I like Tata Martino. He is a great coach... He gets his teams playing well and we all respect him.''
Gerardo Martino factfile
1962: Born November 20 in Rosario, Argentina.
1980-90: The attacking midfielder joins Argentinian club Newell's Old Boys and makes 392 league appearances, scoring 35 goals in 10 years. He wins the Primera Division in 1988.
1991: Spends a year playing for Tenerife and earns his one Argentina cap under Alfio Basile.
1991-94: Returns to Newell's Old Boys for three years and wins two more Argentinian titles.
1994-95: Represents Lanus for one season before returning to Newell's Old Boys.
1996: Enjoys short spells with Ecuadorian club Barcelona Sporting Club and then O'Higgins of Chile.
1998: Takes first coaching job with Brown de Arrecifes.
1999: Joins Platense as coach.
2000: Works as Instituto's head coach.
2002-03: Leads Libertad to two Paraguayan titles.
2004: Claims his third Paraguayan title with Cerro Porteno.
2005: Spends a season with Colon.
2005-06: Returns to Libertad and wins his fourth Paraguayan title in 2006.
2007: February - Becomes Paraguay national team coach and is named South American coach of the year.
2010: June - Takes Paraguay to the World Cup in South Africa and guides the nation to the quarter-finals, where they are beaten by eventual winners Spain.
2011: After Paraguay lose the Copa America final to Uruguay, he steps down as national team manager.
2012-13: Returns to Newell's Old Boys as manager and wins the Clausura in 2013.
2013: July 23 - Agrees two-year contract to become head coach of Barcelona, replacing Tito Vilanova.