Alan Johnson has been appointed to the key role of shadow chancellor in Ed Miliband's first shadow cabinet.
Ed Balls is shadow home secretary while his wife Yvette Cooper - who topped the ballot of Labour MPs for the shadow cabinet - is shadow foreign secretary.
Both had been tipped for the economic portfolio shadowing Chancellor George Osborne.
Mr Miliband said: "I am delighted with my new shadow cabinet, drawn from a broad range of talents across our party.
"My team is united in one central mission for the future - to win back the trust of the British people and take Labour back to power.
"Together, this new generation of Labour will work together to reject the pessimism of this coalition Government as we set out our vision of what Britain can achieve.
"Our values are those of the British people, and this shadow cabinet will ensure that the hopes and concerns of working families are at the heart of our offer to the country."
Other key appointments were another defeated leadership candidate Andy Burnham as shadow education secretary, Jim Murphy as shadow defence secretary and deputy leader Harriet Harman as shadow international development secretary.