It turns out I was wrong about breezy and likeable Charlie being the first perfume to be advertised with an image of a woman wearing pants. Before Revlon Charlie (1973), there was Estée Lauder Estée (1968), and sandwiched in-between was Dior Diorella. If there was another one before them, or around the same time period, please let me know. I believe I've sampled Diorella before, but I have no recollection of the scent apart from it being a citric eau de cologne type, maybe like Eau de Rochas. Since I can't do it justice, please visit Yesterday's Perfume for a great in-depth review.
Edited to add on Jan. 6, 2013 at 12:45 am: According to British paper The Independent, René Gruau's illustration for the Diorella ad was done in 1972 (link to Diorella, René Gruau, 1972, Private Collection - René Gruau: Illustrating Dior, The Independent). Unless Revlon Charlie's 1973 launch year is wrong, Christian Dior Diorella is the first perfume advertised with an image of a woman wearing pants. The perfume ad for Estée Lauder Estée featuring a model in pants appears to have been created around the time of the Star Wars movie, circa 1977.