This photograph by William Henry Fox Talbot is one of the earliest known photographic portraits printed on paper. The woman is in this photograph is his wife Constance, who herself has been credited as the first woman to ever take a photograph (around 1840).
This photograph is a Salted paper print from a Calotype negative, created in October of 1840.
Henry Fox Talbot
Portrait of Constance Talbot, 1840