Understanding the chemical and charge transport properties of grain boundaries (GBs) with high point defect concentrations (beyond the dilute solution limit) in polycrystalline materials is critical for developing ion-conducting solids for electrochemical energy conversion and storage. Elucidation and optimization of GBs are hindered by large variations in atomic structure, composition, and chemistry within nanometers or Ångstroms of the GB interface, which limits a fundamental understanding of electrical transport across and along GBs. Here we employ a novel correlated approach that is generally applicable to polycrystalline materials whose properties are affected by GB composition or chemistry. We demonstrate the connection between the nanoscopic chemical and transport properties of individual boundaries and the macroscopic ionic conductivity in oxygen-conducting Pr0.04Gd0.11Ce0.85O2-δ. The key finding is that GBs with higher solute concentration have lower activation energy for cross-GB ion conduction through a polycrystalline conductor. The resultant semiempirical framework presented here provides a tool for understanding, designing and optimizing polycrystalline ionic conductors.