Pictures taken by Princess Catherine showed the smiling two-year-old outside her Kensington Palace home in London before she set off to begin at the nearby private Willcocks Nursery School.
The princess will be a full-time pupil at the nursery in London which charges £3,000 ($NZ5666) per term.
Charlotte is fourth-in-line to the throne behind her father, her elder brother George and grandfather Prince Charles.
Her parents are expecting a third baby in April.
