Salts containing triarylphosphine radical cations 1(center dot+) and 2(center dot+) have been isolated and characterized by electron paramagnetic resonance (EPR) and UV-vis absorption spectroscopy as well as single-crystal X-ray diffraction. Radical 1(center dot+) exhibits a relaxed pyramidal geometry, while radical 2(center dot+) becomes fully planar. EPR studies and theoretical calculations showed that the introduction of bulky aryl groups leads to enhanced p character of the singly occupied molecular orbital, and the radicals become less pyramidalized or fully flattened.