The electrical properties of polycrystalline graphene grown by chemical vapor deposition (CVD) are determined by grain-related parameters—average grain size, single-crystalline grain sheet resistance, and grain boundary (GB) resistivity. However, extracting these parameters still remains challenging because of the difficulty in observing graphene GBs and decoupling the grain sheet resistance and GB resistivity. In this work, we developed an electrical characterization method that can extract the average grain size, single-crystalline grain sheet resistance, and GB resistivity simultaneously. We observed that the material property, graphene sheet resistance, could depend on the device dimension and developed an analytical resistance model based on the cumulative distribution function of the gamma distribution, explaining the effect of the GB density and distribution in the graphene channel. We applied this model to CVD-grown monolayer graphene by characterizing transmission-line model patterns and simultaneously extracted the average grain size (~5.95 μm), single-crystalline grain sheet resistance (~321 Ω/sq), and GB resistivity (~18.16 kΩ-μm) of the CVD-graphene layer. The extracted values agreed well with those obtained from scanning electron microscopy images of ultraviolet/ozone-treated GBs and the electrical characterization of graphene devices with sub-micrometer channel lengths.