The 35-year-old, who helped River come back from relegation last year, will be at Newell's on loan for a year having recovered from knee surgery in May.
"This is a very special day for me. A month ago River told me they wouldn't be counting on me," Trezeguet told reporters after signing for Newell's in the team's home city of Rosario.
"So, (it's special) to sign for the last champions of Argentine football and an admirable performance in the Libertadores Cup, with a coach who's off to take charge of the best team in the world."
Newell's reached the semi-finals of South America's top club tournament under Gerardo Martino, who on Monday became the leading candidate to take over at Spanish champions Barcelona.
Trezeguet is expected to take on the mantle of Argentina striker Ignacio Scocco, top scorer in the league with 24 goals last season, who has left Newell's for Brazil's International.
He realised a dream playing for River, whom he has supported since his childhood in Buenos Aires, and had worked hard to get fit for the season starting on August 2 before his hopes were dashed when coach Ramon Diaz said he was not in his plans.
At Newell's, Trezeguet said he can realise another dream of playing in the Libertadores Cup and "scoring the few goals I need to reach 300 in my career."
Trezeguet missed a large part of last season in which River finished second in the "Final" championship won by Newell's last month due to knee trouble that required surgery.
Diaz is rebuilding his River squad for a tilt at the "Inicial", first of two championships in the 2013/14 season.
(Additional reporting by Luis Ampuero; Writing by Rex Gowar in London; Editing by Alison Wildey)
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