The micromorphology of three-dimensional (3D) printed silver/polylactic acid (PLA) exposed to heat treatment is reported. The PLA samples were printed through fused deposition modeling and then coated using a conductive silver paint. They were then heat treated in an electric furnace at 5, 10, and 20 min at 100°C. The samples were then characterized using X-ray diffraction, X-ray photoelectron spectroscopy, low-resolution and high-resolution scanning electron microscopy, atomic force microscopy, and roughness analyses. The results revealed that there is transformation of the structure and morphology of the silver/PLA samples on exposure to heat treatment at different times. On heat treatment, the PLA structure transforms from unstable δ state to thermally stable state (α). A slight shift of the 2θ for each peak was observed at heat treatment. There are shifts up to 0.7 eV on the binding energy of the Ag3d as shown by the X-ray photoelectron spectroscopy analysis, indicating an enhancement of bonding of silver onto the PLA structure on thermal treatment. The surface appearance was described by root mean square roughness, mean roughness, skew, kurtosis, and fractal dimension. The inner structure of the samples is shown by scanning electron microscopy at cross sections. The morphology and topography on the surface of the silver/PLA samples indicate a considerable structure growth and adhesion between the silver and PLA. These results illustrate that in situ deposition of silver paint onto PLA substrate, and subsequent heat treatment can be explored as a viable process for enhancing metallization of 3D printed polymer parts for various applications.