Microstructural and electrical properties of Gd-doped CeO2 (GDC; Ce0.9Gd0.1O1.95) thin films prepared by pulsed laser deposition as an electrolyte in solid-oxide fuel cells (SOFCs) were investigated. The GDC thin films were prepared on various substrates including single-crystal yttria-stabilized zirconia (YSZ) and magnesium oxide (MgO) substrates. The GDC thin-film electrolytes with different grain sizes and grain morphologies were prepared by varying the deposition parameters, such as substrate temperature, oxygen partial pressure, target repetition rate, and laser ablation energy. The microstructural properties of these films were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Alternating-current (AC) and direct-current (DC) electrical measurements through in-plane method show that the electrical property of the GDC thin film strongly depends on grain size, e.g., the total conductivity of the films deposited at 700 °C (7.3 × 10−3 S/cm) is about 20 times higher than the ones deposited at room temperature (3.6 × 10−4 S/cm) at the measurement temperature of 600 °C.