Singh bid adieu as Prime Minister of two terms in a televised address where he said the judgement delivered by the people in the elections should be respected by all and wished the incoming government every success.
The 81-year-old economist, credited with playing a key role in ushering in economic reforms in the 1990s, leaves a mixed legacy of achievements and failures during his tenure.
Mukherjee accepted the resignation and requested him and his colleagues to continue till the new government is formed.
Earlier this morning, the Cabinet met and recommended dissolution of the Lok Sabha. The Cabinet adopted a resolution lauding the role of Singh.
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Looking back, he said India saw many successes and achievements "that we should be proud of" and the country has become far stronger in last one decade. But it still has vast latent development potential.
"I address you today for the last time as Prime Minister of India. Ten years ago, when I was entrusted with this responsibility, I entered upon it with diligence as my tool, truth as my beacon and a prayer that I might always do the right thing," Singh said in his brief address to the nation.