Ms Phillipson said she wanted to put education “back at the forefront of national life” and “transform the image” of teaching.
The DfE said this was key to fixing the crisis in the recruitment and retention of teachers.
Ms Phillipson said writing to workforces on Monday was her “first priority”.
She said the teaching profession had been “talked down, sidelined and denigrated” for too long.
Teaching unions had strained relations with the previous government and several days of strikes took place across the UK last year over pay.
It is not yet clear what the pay offer will be for teachers this year but unions have welcomed Ms Phillipson’s appointment.
Daniel Kebede, general secretary of the National Education Union (NEU), said it was “absolutely vital” the relationship between ministers and the teaching profession was reset.
“After the chaos of recent times, NEU members are hopeful that Bridget Phillipson will usher in a period of stability and seriousness at the Department for Education,” he added.
He called for Ms Phillipson to immediately publish the 2024/25 pay and funding offer for schools to right the “first of many wrongs” of the previous government.
Paul Whiteman, general secretary of the National Association of Head Teachers (NAHT), congratulated Ms Phillipson on her appointment but said “we should not underestimate the scale of the task the new government will now face”.
“NAHT stand ready to work with the new government and we look forward to working with Bridget and her team in years ahead,” he said.
