Pentagonal bipyramid-shaped gold-rich Au/Ag alloy nanoparticles are synthesized in ethylene glycol (EG) in the presence of small amounts of AgNO3 and PVP without using Au seeds. The contents of Au and Ag in pentagonal nanobipyramids are determined by energy-dispersive X-ray spectroscopy (EDS). The EDS data demonstrates that this kind of nanoparticles is composed of Au/Ag alloys, not silver monolayers simply covering the surface of Au nanoparticles. Insights into the growth mechanism of pentagonal bipyramid-shaped gold-rich Au/Ag alloy nanoparticles are discussed.