The 31-year-old joined Sevilla from PSV in 2019 and scored 19 goals in 94 appearances, including a brace in the club's 3-2 win over Inter in the 2020 UEFA Europa League final.
He joined Barcelona on loan last season and featured 29 times, but the seven goals netted were not enough to persuade Xavi's side of making a permanent move for the striker.
Rather than return to Sevilla for the 2022-2023 campaign, the Netherlands international has instead re-joined Eredivisie side PSV on a three-year deal.
PSV and Sevilla both confirmed the transfer on their official websites, with reports from Spain valuing the transfer in the region of €4 million ($6.1 million).
De Jong scored more than 100 goals for PSV in his previous five-year stint at the club, helping his side to three league titles, and is excited to be back in Eindhoven.
"I'm home again. That's how it really feels," De Jong said. "I can't wait to score goals for PSV again and hope to see the whole stadium jump again after that.
"Great things can happen this season together. In all the years I played here, we went for the title. It seems logical to me that I want to do that again.
"In addition, I want to enter the Champions League with PSV. It is fantastic to be able to play football on that podium."
De Jong, who had been linked with numerous other clubs, added: "It gives a great feeling to return. In recent weeks I read that many fans were hoping for it.
"This choice was not very difficult for me to make. The club is building something very beautiful and I want to be part of that. It feels like something great is about to happen here."
De Jong, capped 38 times by Netherlands, has also previously won the Eredivisie and Dutch Cup with Twente.
He joins the likes of Xavi Simons, Walter Benitez and Ki-Jana Hoever in joining PSV, which is now managed by Ruud van Nistelrooy.