Defoe was named as the permanent successor to Neal Ardley, who was sacked earlier this month. The 43-year-old will be assisted by ex-Sunderland midfielder Paul Bracewell.
Defoe has long been in the market for a head coach breakthrough and has been keen on the Sunderland job in the past. He has previously been a coach in Tottenham's academy and briefly worked in a caretaker role at Rangers in 2021 as part of a four-man coaching team.
Woking are 11th in the National League and host Altringham on Tuesday night, which Defoe will watch from the stands.
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The former striker said: “Woking is a historic club with huge potential, and I’m thrilled to be part of this exciting project. I can’t wait to get started.”
Woking chairman Todd Johnson said: “Jermain’s achievements as a player speak for themselves, but what stood out to us during the process was how he sees the game, how he drives standards, and his approach to leadership and player development.
“We have a clear plan for where we want to go as a club, and we believe Jermain is the right person to build on the strong foundations already in place and help take us forward in the next phase of that journey.”
Defoe will be joined by assistant coach Bracewell, while interim bosses Craig Ross and Jake Hyde will continue to be part of the backroom team alongside Dale Gorman. Ross and Hyde will take charge of Tuesday’s home league game against Altrincham.
Woking's director of football Jody Brown said: “Jermain’s love of the game, his determination to succeed and his alignment with our preferred playing philosophy were important.
“These are shared values in terms of the working environment, player development, and high-performance culture. He has a real appreciation for the club, the staff, the players, and what we’re building here.”