Prince George can be seen smiling and holding his sister's hand, and affectionately kissing her on the forehead.
Another of the shots shows the siblings looking away from the lens.
The images were taken by their mother, the Duchess of Cambridge, at their family home, Anmer Hall in Norfolk.
It's thought the pictures were captured a few weeks ago when Charlotte was around two weeks old.
They have been released just days after the family announced Princess Charlotte would be Christened by the Archbishop of Canterbury on July 5th.
The service will take place at St Mary Magdalene Church in Sandringham.
Archbishop Justin Welby said: "I am delighted to be invited to conduct the baptism of HRH Princess Charlotte.
"It will be an extraordinary honour and privilege to help welcome the Princess into the family of the church.
"Along with her parents and all her family, I look forward to joining in this joyful day of celebration and thanksgiving."
The images were previewed on the Kensington Palace Twitter account and have been retweeted thousands of times.