Discrete nanoparticles of MnAs with distinct magnetostructural properties have been prepared by small modifications of solution-phase arrested precipitation reactions. Rietveld and X-ray atomic pair distribution function based approaches were used to explore the evolution of the structure of the samples with temperature, and these data were compared to the magnetic response measured with ac susceptibility. Relative to a bulk standard, one type of MnAs nanoparticles was found to demonstrate similar but smaller structural transitions and corresponding magnetic changes. However, both magnetic and structural transitions in the second type of nanoparticles are strongly suppressed. © 2011 American Chemical Society.