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"I love you @laurenzima," he captioned a slideshow of photos from the proposal, which took place at Brand Napa Valley in California.
"The next chapter starts now!" added Harrison, who wiped his Instagram account clean.
Zima, 33, also shared the news on her account.
"We tell each other this all the time, and we said it again in an unforgettably beautiful moment this weekend: I didn't know love could be like this," she wrote. "You are the most incredible partner. Thank you for loving me, championing me and asking me to marry you. Here's to the next amazing chapter, and all the rest."
The engagement news comes almost five months after Harrison's official exit from the Bachelor franchise. The longtime host came under fire earlier this year for his response to then-Bachelor contestant Rachael Kirkconnell's past racially insensitive behavior, which had resurfaced online while Matt James' season was airing and engulfed the franchise in controversy.
"Chris Harrison is stepping aside as host of The Bachelor franchise," Warner Horizon and ABC Entertainment said in a joint statement on June 8. "We are thankful for his many contributions over the past 20 years and wish him all the best on his new journey."
Added Harrison, "I've had a truly incredible run as host of The Bachelor franchise and now I'm excited to start a new chapter. I'm so grateful to Bachelor Nation for all of the memories we've made together. While my two-decade journey is wrapping up, the friendships I've made will last a lifetime."
Harrison, who previously appeared as a recurring guest on ET's Bachelor segments, told PEOPLE in 2019 that Zima made him "happy."
"It's been easy and I think that's how it all starts," he said. "We started dating and, like any relationship, she made me happy. She was kind, nice, we got along, she blended in great with my friends, and just all those steps in the relationship where you start checking those boxes off and it gets better and better and better."
The TV personality was previously married to college sweetheart Gwen Harrison for 18 years. The pair — who share two kids, Joshua and Taylor — announced their divorce in 2012.