Between 1880 and 1884, Macpherson studied in Switzerland, under the artist Auguste-Henri Berthoud. In 1885, she returned to Edinburgh and exhibited at the Royal Scottish Academy for the first time. Macpherson began to exhibit her work at the Glasgow Institute of the Fine Arts from 1887 onwards.
In 1889, Macpherson moved to Paris. Once there, she trained under Gustave Courtois and Pascal Dagnan-Bouveret at the Academie Colarossi. Whilst in France, Macpherson also worked at the artists' colony of Concarneau during 1891, where she began to specialise in paintings of girls in traditional Breton costume.
Macpherson was dividing her time between France and Scotland, where she had a successful career as a portrait painter. She shared a studio in Edinburgh with another artist, Josephine Hoxie Bartlett. Macpherson and Bartlett became members of the Society of Scottish Artists in 1892.Macpherson and Bartlett had a joint exhibition in Edinburgh in 1895. They moved permanently to Paris in 1899.
Throughout her career the following art societies all accepted paintings by Macpherson:
Royal Scottish Academy
Glasgow Institute of Fine Art
Society of Scottish Artists
Société Nationale des Beaux-Arts
Royal Academy, London
Société des Artistes Français
Bronze medal - Exposition universelle, Paris, in 1900
Gold medal - Exposition nationale, Reims, in 1903
Gold medal - Exposition internationale, Nantes, in 1904