In this study, samarium (Sm-10at%)-doped BiFeO3 (SmBFO) thin films were grown on platinum-coated glass substrates using pulsed laser deposition (PLD) to unveil the correlation between the microstructures and nanomechanical properties of the films. The PLD-derived SmBFO thin films were prepared under various oxygen partial pressures (PO2) of 10, 30, and 50 mTorr at a substrate temperature of 600 °C. The scanning electron microscopy analyses revealed a surface morphology consisting of densely packed grains, although the size distribution varied with the PO2. X-ray diffraction results indicate that all SmBFO thin films are textured and preferentially oriented along the (110) crystallographic orientation. The crystallite sizes of the obtained SmBFO thin films calculated from the Scherrer and (Williamson–Hall) equations increased from 20 (33) nm to 25 (52) nm with increasing PO2. In addition, the nanomechanical properties (the hardness and Young’s modulus) of the SmBFO thin films were measured by using nanoindentation. The relationship between the hardness and crystalline size of SmBFO thin films appears to closely follow the Hall–Petch equation. In addition, the PO2 dependence of the film microstructure, the crystallite size, the hardness, and Young’s modulus of SmBFO thin films are discussed.