The Chicago Tribune reported that Walgreen died in his sleep.
Walgreen, who served as the CEO of the Walgreens chain for nearly three decades, started his career as a stock boy when his father owned the company. After high school, Walgreen went on to earn a pharmacy degree from the University of Michigan.
"He loved to tell such wonderful stories of those first Walgreens stores, with the gas lighting instead of electricity and the old soda fountains," said his grandson Les Walgreen. "It was such a huge and important part of his life."
The first Walgreens store opened in Chicago in 1901 and the chain expanded rapidly throughout the next 20 years.
During World War II, Walgreens established a not-for-profit pharmacy in the Pentagon, which later was formally recognized by President Eisenhower.
The Tribune reported that Walgreen was known as a savvy traveler who, even in his old age, remained very active.
Walgreen is survived by his wife, two sons, one daughter, 10 grandchildren and 9 great grandchildren.