Twickenham, named after the area of London in which it was built in 1907, held its first rugby international in 1910 when England hosted Wales, and will change its name to Allianz Stadium in September.
"(The agreement) will see Allianz and the RFU offer significant support to the grassroots game through financial investment that aims to secure future investment into the community game," the RFU said in a statement.
The sponsorship of the 82,000-capacity stadium is the eighth of its kind for Allianz, and is reminiscent of the renaming of Ireland's Lansdowne Road Stadium which became the Aviva Stadium after the old ground was demolished and a new one built.
Twickenham has hosted England men's games since 1909.
The 82,000-seater stadium also hosts international women's matches, key domestic games, community events and music concerts.
The RFU have been looking for additional investment and, in a document seen by the BBC, were considering selling their south west London home and buying a 50 percent share in Wembley.
The Twickenham Stadium Masterplan Programme (TSMP) revealed the RFU board discussed the proposal in March last year but no formal approach was made to the Football Association (FA).
Those plans were shelved in favour of redeveloping the stadium and the RFU say the move will provide a "significant, long-term investment in the game".
"This is an opportunity to celebrate our stadium's proud legacy while developing it for the future," said RFU chief executive Bill Sweeney.
"This partnership will support us in moving the game in a direction which serves all rugby, from minis to the elites, from club coaches to our national coaches and everything in between."
The venue will host the final of the 2025 Women's World Cup, while the first international fixture under the new name will see England's women play world champions New Zealand on 14 September.
-Reuters/BBC