“Sally and Mrs. Reed”, taken ca. 1853 by amateur Mary Dillwyn, one of the earliest of female Welsh photographers.
For those further interested, there is a gallery of her photographic work at the Early Swansea Photography website.
I guess that just shows there really is nothing new under the sun. Now let’s find the first selfie.
Although I don’t usually give much weight to Huffington Post, this is a possibility (or possibly one of them on the link in the article).
http://www.huffingtonpost.com/2013/12/05/worlds-first-selfie-1839-robert-cornelius_n_4392804.html