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Control over the synthesis of anisotropic nanoparticles is crucial as slight differences in their size, shape, sharpness, or the number of tips in the case of gold nanostars, has an inordinate influence on their properties and functionality for future applications. Herein, we show that the supplier and purity of polyvinylpyrrolidone (PVP) can significantly alter the synthesis of gold nanostars, demonstrating that impurities, not PVP itself, are the main factor responsible for star-like shape formation. We demonstrate that in the presence of pure PVP and N , N -dimethylformamide, the use of hydrazine leads to the formation of branched nanoparticles. This synthetic approach opens the door to solving issues associated with the use of commercial PVP during the synthesis of gold nanostars., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)