The Argentinian Football Association executive committee met in Buenos Aires to finalise the 48-year-old former World Cup winner's appointment, BBC reports.
Carlos Bilardo, who was coach when Maradona lifted the World Cup in 1986, will assist him as general manager.
"It's a a special day for Argentinian football," AFA president Julio Grondona said. Maradona replaces Alfio Basile, who stepped down for personal reasons.
"He's anxious to start, to see the players and talk to everyone, both those who play in Argentina and those who play abroad," Bilardo said.
Maradona, whose official title is technical director, had been expected to visit Britain ahead of Argentina's match against Scotland at Hampden Park on 19 November.
It was thought he would attend Liverpool's Champions League match with Atletico Madrid and meet Javier Mascherano, followed by Manchester United's Carlos Tevez at the weekend, but that trip has been abandoned.
"We are going to play the game against Scotland with the best team we've got," said Maradona, who will stay in Argentina and formulate plans for his first match in charge.
Maradona, who has had two brief spells as a club coach in Argentina, scored his first goal for Argentina in their 3-1 friendly win over Scotland at Hampden in 1979
One of the infamous episodes in his playing career saw Maradona score with an outrageous handball against England in a World Cup quarter-final in 1986.
He later described it as the "hand of God" and believes this will endear him in Scotland.
He added: "I'm going to a country where they adore me because of the goal against the English.
"The English and the Scots get on horribly - serious bad blood.
"But now we are going to play a game against Scotland, where they are going to treat us well."
If Maradona does take over he will succeed Alfio Basile, who resigned earlier this month after a World Cup qualifying defeat by Chile.
Argentina and Barcelona star Lionel Messi will not play against Scotland next month as he was allowed to go to the Olympics by the Spanish club.
But Messi has welcomed Maradona's expected appointment, despite being recently criticised by the Argentine legend for his attitude on the pitch.
"Those are things that you say at the time. I know Diego appreciates me and I don't hold any grudges," Messi told Italy's Gazzetta dello Sport newspaper.
"There's no problem. He's a great and I admire him for what he gave to Argentine football."
Maradona spent seven seasons at Italian Serie A side Napoli and the club's former president, Corrado Ferlaino, insisted the Argentine was effectively the coach on the pitch.