New coach Paul Roos made the announcement at the Melbourne Cricket Ground on Wednesday.
Dual best and fairest winner Jones, 26, was widely considered to be the leading choice for the role, after Jack Trengove stepped down at the conclusion of the 2013 campaign.
Jones' appointment comes after a controversial era for the captaincy of the country's oldest football club, with Trengove and Grimes sharing the role in 2012 and 2013.
Appointed by coach Mark Neeld at 20 years of age, Trengove was the youngest captain in VFL/AFL history and held the role with Grimes during two of the club's toughest seasons.
Across 2012 and 2013 the Demons won just six matches, with Trengove's form noticeably down on his first two seasons.
The six-man leadership group also includes James Frawley, Colin Garland, Mitch Clark and Trengove.