The Leverkusen captain, capped 26 times by Germany, has been with the club since 2005 and has opted against extending his contract beyond its June 2015 expiry date.
"The decision to quit in the next year as a player is not easy for me," the 32-year-old told the club's official website.
"However, I was open-minded about many things during my whole 15 years in professional football and also investigated other interests.
"I now think the time has come to make a cut and me develop both professionally and personally.
"The time in Leverkusen was formative for me. Bayer 04 are German giants with regular international presence, here I have become a national player, here I was able to enjoy the Champions League.
"In the summer I'm going to look back on a great and eventful time at Bayer 04."
Rolfes missed almost three months of action this season after undergoing ankle surgery and has not completed 90 minutes in the Bundesliga this term.
Sporting director Rudi Voller said that "all doors are open" for Rolfes to return to Leverkusen in a coaching capacity.
