Liz Moore, the LPGA's corporate secretary, will serve as interim commissioner until a replacement is named.
"I'm proud of the unprecedented growth the LPGA has enjoyed since I began my tenure," said Marcoux Samaan, the LPGA's ninth commissioner.
"The strategy we have built for growth and impact along with the infrastructure we have added to capitalize on the tremendous opportunity ahead will serve the LPGA well in the coming decades."
Marcoux Samaan's tenure included the LPGA's largest period of growth, including a 90 percent jump in prize money and record player earnings, doubling for the top 100 players from just over $570,000 in 2021 to more than $1 million in 2024.
The women's tour enjoyed record attendance in 2024 and the LPGA Foundation boosted the number of women and girls playing golf.
"I'm confident the LPGA is well-positioned for continued success as we build on the growth trajectory of the past three and a half years of Mollie's leadership," LPGA board chair John B. Veihmeyer said.
