An energy-dispersive spectrometer with a superconducting transition edge sensor (TES) microcalorimeter mounted on a scanning transmission electron microscope (STEM) is developed to enhance the accuracy of nanoscale materials analysis. TES microcalorimeters generally have sensitive surface areas of the order of 100×100 µm 2. Also, the magnetic field generated by the STEM objective lens means that a TES microcalorimeter cannot be placed in a STEM column. We therefore use polycapillary optics to collect the X-rays. In this study, X-rays are collected from a STEM specimen and are then focused on a silicon drift detector; from these measurements, the optics are characterized and the experimental results are compared with the design of the optics.