It rivals a recent collaboration between Sainsbury's and British Gas, which have clubbed together to offer a number of services.
The tie-up between E.ON and Tesco means E.ON customers will be able to exchange their Clubcard vouchers for Clubcard tokens, which are redeemable on their energy bill.
As part of the initiative, 50% will be added to the value of any Clubcard vouchers used to pay for energy bills, meaning for every £10 worth of vouchers exchanged, £15 will be deducted from the customer's bill.
The smallest amount redeemable is £5 worth of Clubcard vouchers, so that £7.50 would be taken off a customer’s bill.
Tesco and E.ON have been in partnership for 13 years, with eligible E.ON customers able to earn Clubcard points for money spent on energy.
Graham Bartlett, managing director of E.ON Energy Solutions, said: "We're extremely proud that we’re the only energy supplier to allow customers to earn Tesco Clubcard points on their bills and also use Clubcard vouchers as a new way to pay.
Janet Smith, Tesco's Clubcard director, said: "Customers tell us that money is tight, so being able to offer them a new way to save money on energy bills is really important.
Tesco is currently looking to expand the Clubcard scheme at home and oversees. It recently promoted Janet Smith to its work level five, one below the company's main board. It has also created three new Clubcard director roles.