We combine the characterization techniques of scanning AC nanocalorimetry and x-ray diffraction to study phase transformations in complex materials system. Micromachined nanocalorimeters have excellent performance for high-temperature and high-scanning-rate calorimetry measurements. Time-resolved X-ray diffraction measurements during in-situ operation of these devices using synchrotron radiation provide unprecedented characterization of thermal and structural material properties. We apply this technique to a Fe0.84Ni0.16 thin-film sample that exhibits a martensitic transformation with over 350 K hysteresis, using an average heating rate of 85 K/s and cooling rate of 275 K/s. The apparatus includes an array of nanocalorimeters in an architecture designed for combinatorial studies.