Colossal magnetoresistance (CMR) materials are promising for spintronics, which uses spins instead of charges to transfer information. However, the application is currently limited by the low transition temperature and large magnetic field required. In this thesis, we use high-energy electrons as a probe to directly observe these materials on the atomic scale. The short wavelength and strong interaction of electrons with atoms allow us to look at the materials with high spatial resolution and high sensitivity. Our developed experimental and analysis techniques provide new insights into the structure-properties relationships of such CMR materials.