We really do know a lot about Napoleon’s daily habits from the memoirs by Napoleon’s secretaries. They were the ones who had to follow his workday - somewhat.
There was Napoleon at war and Napoleon not at war. I’ll only discuss Napoleon not at war. At war, it seems he was constantly working except when he was eating or dozing off wherever he could.
Napoleon’s “levee” was at 9am. Anyone entitled to the right to approach him then could. This would be top level officials like Maret, the Secretary of State.
After he spoke to whomever required his attention he went to his “closet” or “cabinet”, what we’d call his office. Then he’d go through his mail with his secretary. Napoleon would throw things he didn’t have to deal with on the floor calling that the “answered” file. He’d work straight through until lunch where he usually left his spouse waiting for about an hour. Then he’d go back to work. He’d continue until dinner where he usually left his spouse waiting about an hour.
After dinner, he do the chit chat small talk, table game thing they did at night in the palace. Napoleon would sleep at 10pm. He’d get up at 2am. He’d work until dawn, take a bath and then be ready for the levee by 9am the next day.
That was the general pattern described by Napoleon’s secretaries.
My source information is freely available here.