Thermoelectric materials convert thermal energy to electrical energy (and vice versa) in solid state. They can be used for thermometry, localized heat pumping, and power generation. Our prior work demonstrated results for laser powder bed fusion of semiconductor thermoelectric materials (bismuth telluride, zirconium nickel stannide, and magnesium silicide). The temperature-dependent electrical transport properties and Seebeck coefficient were characterized from room temperature to 500°C, and the results showed variation in transport properties when the material is laser processed versus traditional hot pressing. In this work, we report on the structural modifications induced by laser processing which give rise to the varied carrier transport behavior. Using electron microscopy, X-ray diffraction, and Raman spectroscopy, we investigate both microstructure and phase to find the structural heterogeneity which impacts carrier transport. The results provide a fundamental understanding of the relationship between laser processing, microstructure, and carrier transport properties for both doped and undoped bismuth telluride.