Macron, a French and drama teacher until 2015, has accepted a supervisory and teaching role for two schools being built, one in a suburb of Paris and another in a rural area of southeast France.
On Monday, she visited the first of the schools by the "Institut des Vocations", which is also backed rap star Ben J and celebrity chef Thierry Marx and is being financed by French luxury giant LVMH.
The school in the poverty-wracked Clichy-sous-Bois suburb in northeast Paris will open its doors in September along with another facility near Valence in southeast France, offering courses to around 50 school dropouts aged 25-30 every year.
"It won't be like the lessons that I gave to pupils before, but more in the Anglo-Saxon style, interactive," the 66-year-old, who taught at prestigious private schools in her home town of Amiens as well as in Paris, told reporters.
She said the school aimed to give its students, who will be paid 1,000 euros (1,100 dollars) a month, "the foundations to be able to enter the workplace.
"We know they need to know the four operations in maths, to know how to write French, to express themselves, to construct arguments in a written text. I want to give them a taste for literature," she added.
Brigitte met Emmanuel Macron, 41, while he was a student in her school in Amiens and began a relationship with him while he was still a teenager, causing a minor scandal locally and anger in their families.
The mother-of-three said that other private companies were interested in following the example of LVMH and sponsoring other adult schools, which are designed to tackle France's chronic high unemployment rate.
"We are going to duplicate it," she said, adding that oil group Total had expressed an interest in investing in others.
Brigitte Macron has kept a low public profile since her husband's election victory in May 2017, accompanying him for major state events but giving few interviews.
She became entangled in an early public row shortly after he took office over plans to create a formal public position of first lady, which would have given her an office and a budget -- an idea Macron abandoned under pressure.
The lover of theatre and literature, who remains political advisor to her husband behind the scenes, had announced that she intends to devote her time to her twin causes of education and helping the handicapped.
Rapper Ben J -- real name Fabien Loubayi -- said the new schools aimed to provide opportunities "to the invisible, people I see during my concerts. It's important to offer them a hand up, to give them confidence in themselves."