Aung San Suu Kyi will reportedly head up foreign affairs, energy, education and be minister in Myanmar’s new cabinet.
Aung San Suu Kyi is barred from the presidency herself and had been widely expected not to take a ministry.
Her name was on a list of 18 submitted to parliament by President-elect Htin Kyaw.
There are no other women appointed to the cabinet.
Myanmar’s constitution, drafted by the outgoing military rulers, prevents Aung San Suu Kyi from becoming president because her two sons have British passports.
President-elect Htin Kyaw is Aung San Suu Kyi’s close ally, and she previously said that she would be “above the president” anyway, governing through a proxy.
The cabinet announcement came as a surprise – many had assumed that Aung San Suu Kyi would control the government from the outside.
If Aung San Suu Kyi does become foreign minister, under the complex political structure she will have to stand down as a lawmaker and refrain from all NLD activities.
Fifteen of the names on the list were chosen by Aung San Suu Kyi, a Nobel laureate and former political prisoner, and three by the commander-in-chief of the army.
Parliament is expected to vote later in the week to confirm the posts.
After his election last week, Htin Kyaw said his appointment was “Aung San Suu Kyi’s victory”.
The NLD has a huge majority in both houses of parliament, despite the military occupying 25% of seats, so the candidate it backed was all but guaranteed to win.
Despite weeks of negotiation prior to the vote in parliament, the NLD was unable to persuade the military to remove or suspend the clause that prevented Aung San Suu Kyi taking office.