Miller notified the England and Wales Cricket Board of his wish to step down from his role during the home Investec Ashes Series in 2013.
The 61-year-old - who played 254 first-class fixtures for Derbyshire between 1973 and 1986, before ending his career back in Derby in 1990 - has been in the job for the last six years during which England have won three successive Ashes series.
Miller said: “It will be sad to step down after a 14-year period as first an England Selector and then the National Selector.
“However I feel that this is the perfect time to hand over the reins and I cannot think of anyone more suitable than James Whitaker to assume control of the selection panel.
“I wish him, Andy Flower, Ashley Giles and all the England players the very best of in the years ahead and I am sure that they will continue the pathway to success not only this winter but also in the years to come.”
Derbyshire County Cricket Club Chairman Chris Grant added: “Many congratulations on a job well done as National Selector to Geoff Miller.”
ECB Chief Executive David Collier concluded: “Geoff Miller has been an exceptional National Selector presiding over selection during one of the most successful periods in England’s cricket history.
“He developed an excellent relationship with the Counties and with the England management team and he will be greatly missed by everyone at ECB. England cricket owes a great debt of gratitude to Geoff for the outstanding contribution he has made to the game and to the fortunes of our national team.”
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