The aim of this study is to characterize the grain boundary microstructure of artificial La0.67Sr0.33MnO3 (LSMO) grain boundaries obtained by epitaxial growth on SrTiO3 (STO) bicrystal substrates. The films were deposited on STO bicrystal substrates using pulsed laser deposition. The substrates were (001) oriented and the boundaries were symmetrical [001]-tilt boundaries with nominal tilt angle 24° and 37° respectively. The microstructures were characterized using a transmission electron microscope. The thickness of the LSMO films was 32 and 37 nm respectively. The films were relatively smooth and the interface between the substrate and the films was sharp without any evidence of chemical reaction or interdiffusion.