Hearts will have their shirts sponsored by national charity Save the Children for the next three years.
It is the first time a British club has agreed a permanent shirt sponsor with a national charity - although Aston Villa were sponsored by local hospice Acorns during the 2008-09 season.
The deal has been funded by an anonymous "group of philanthropists", said Hearts owner Ann Budge.
A seven-figure sum will be split evenly between Hearts and the charity.
"Through their enormous generosity they have agreed to provide funds at a level which more than removes the need for a commercial shirt sponsor," added Budge.
Barcelona have a deal with the United Nations Children's Fund (Unicef) until 2016 - the charity has featured on the front and the back of the Catalan club's shirts.
Of the deal at Hearts, Budge explained: "[The group] indicated that they wanted to offer financial support to the club - and when they asked if there was a specific area in which they could help, the idea was born.
"These business people believe that we are promoting true family values and they want to help.
"It also demonstrates that - with a bit of lateral thinking - things can be done differently in football. We don't have to be constrained by the statement that we hear all too often: 'This is how things are done in football.'"
Hearts say the money will be used to repair key infrastructure at Tynecastle Stadium and strengthen their academy programme.
The Edinburgh club last month secured the Scottish Championship title with seven games to spare, meaning an instant return to the Scottish Premiership, less than a year after exiting administration.