The Czech national team stalwart has signed a one-year contract with the club, whose colours are also defended by compatriots Adam Hlozek and Robin Hranac.
"After years in England at West Ham United, I am now looking forward to a new challenge in the Bundesliga," Coufal told the club's website, before adding:
"The negotiations with TSG were excellent, and I didn't have to think long. I am convinced that the team has great potential, and I want to help us achieve our goals as a team in the coming season."
Coufal is set to replace French defender Valentin Gendrey in the squad, who broke his ankle in training at the end of July, tearing ligaments and facing a long layoff.
"Vladimir is an experienced international and has played in the English Premier League. Thanks to his experience, he will need almost no adaptation period.
"We are convinced that with his excellent mentality and individual qualities, he will be an ideal addition to our team in the coming season," said Andreas Schicker, TSG's sporting director.
Coufal had been playing for West Ham since October 2020, after transferring from Slavia. His contract at the club, where Czech national team captain Tomas Soucek also plays, expired after last season.
Although Coufal wanted to continue in England, where several clubs were interested in him, he has eventually gone to the Bundesliga. At Hoffenheim, he will replace Kaderabek, who left the club after 10 years and headed to Sparta Prague.