Investigation into the thermal behavior of orthorhombic Forms I and II of spironolactone, by means of differential scanning calorimetry and high-resolution X-ray powder diffraction, showed that Form I melts then recrystallizes into Form II at 373–393 K, i.e. in the temperature range within which high resolution X-ray powder diffration showed that Form I transforms into Form II. Refinements of the lattice parameters of the two forms indicated that Form I is denser than Form II in the range from 298 K up to the temperature at which it melts.