The supermodel is shown immersed in a serious discussion in nine black-and-white frames, assembled together as one portrait by Corinne Day.
The images make the 33-year-old look extremely animated and in some cases the worse for wear. They were taken at her home two months ago.
A spokesman for the National Portrait Gallery in London said: "Forming one large work, each element of the portrait reveals a different expression, at times facing the camera head-on, at others in conversation or in quiet contemplation.
"Taken by Corinne Day in December 2006, the portrait brings something new to our perception of the enigma that is Kate Moss, among the most photographed women in the world today."
Day was one of the first to work with Moss after she was discovered at the age of 14. Their first collaboration in Vogue magazine in 1993 featured the model in a council flat in dreary underwear.