The coaching role will be Mascherano’s first, having announced his retirement from football just over a year ago.
Mascherano will come in as a replacement for Fernando Batista, who is joining the backroom staff of the Venezuela national team under new manager Jose Pekerman.
"The 37-year-old former captain of the national team will take up the post from January 2022," The Argentina Football Association said in a statement.
Mascherano started his career with River Plate before turning out for clubs including Brazil’s Corinthians, West Ham United, Liverpool and Barcelona before moving to Hebei China Fortune in 2018.
Mascherano, who is Argentina’s second most capped player with 147 appearances after Lionel Messi, joined Estudiantes, his last club, from Chinese Super League side Hebei China Fortune in January 2020.
His most successful spell in club football was at Barcelona, where he won five La Liga titles, two UEFA Champions League trophies, five Copa del Reys among other honours.
Mascherano was a member of the Argentina side that lost the 2014 FIFA World Cup final to Germany but has two gold medals from the 2004 and 2008 Olympic games.