The Southeast Asian nation was ruled for five decades by a brutal junta that smothered opponents with violence, jail and political sleight of hand.
But in 2011 the junta suddenly handed power to a semi- civilian government led by former generals.
Sweeping reforms since have loosened the straitjacketed economy and brought many freedoms to an isolated, wearied people - including the release of most political prisoners.
Polls open at 6:00 AM (0500IST) and close in the late afternoon with official results expected to start trickling out by early today.
It is the first election the party has contested since 1990, when the NLD claimed a landslide only to see the army ignore the result and condemn Suu Kyi to spend most of the next 20 years under house arrest.
Suu Kyi - affectionately known as "Mother Suu" - towers over the country's democracy movement, acting as a galvanising force for the NLD.
"I will vote for Daw Suu as she is the only one who can bring change for us," Nan Pan Aye, 35, a shop owner in Karen State, told AFP using the honorific "daw".
But the 70-year-old Suu Kyi is barred from the presidency by a constitutional clause believed to have been inserted by the army drafters specifically to hamper her political rise.
She has also faced international censure for failing to speak up for the country's embattled Muslim population - especially the ethnic Rohingya in restive Rakhine State.
But her supporters, many of whom will vote for the first time today, see an NLD win as a stepping stone to the fulfilment of her destiny to lead the country.
Some 30 million people are eligible to vote, with 91 parties standing in more than 300 constituencies.