The 33-year-old, alongside Liam Heath, won bronze at London 2012 in the K2 200m and then upgraded that to silver four years later in Rio.
They are two of Schofield's 24 international medals and he hopes to add to that in his final two World Cup events in Poznan and Duisburg in May, before leaving to become head of performance and pathways at Scottish Canoeing.
"It's been a wonderful career, there's been highs and lows but I've shared a lot of that with a great team, some great coaches, great mentors and friends," he said.
"So I'm moving onto the next level of my life with a bit of a heavy heart, there's always desires to push onto the next level, in this case Tokyo, but I did get the feeling it was time for a new chapter to start for me.
"It will be a privilege to work in sport as a career. Sport has given me so much and I've been looking for a way to be involved in that once I stopped competing. To do that within canoeing is the absolute dream."
Schofield narrowly missed out on selection for the 2008 Games in Beijing and forged his partnership with Heath a year later. In their first season, they became European champions.
From thereon their medal collection consistently grew, with two further European titles and two World Championship medals to go alongside their two Olympic crowns.
"As a crew we had a really successful partnership. We gelled straight away and realised quickly that we had the same approach and mentality to reach our shared goal," Heath said.
"Technically he is exceptional and made it easy for me to do my job, not only in the K2 but also when he trained alongside me in the K1.
"He is a selfless training partner and generous with his time to help other athletes."