*Corresponding author. Email: ji.730@osu.edu

Solid-state batteries (SSBs) with solid electrolytes (SEs) are attracting substantial investment from the automotive industry because of their potential to enable fast-charging and safer next-generation electric vehicles. The microstructure of the SE critically affects battery performance. Electrochemical impedance spectroscopy (EIS) is a powerful, non-destructive probe of charge-transfer and transport processes within SEs and across electrode/SE interfaces. However, quantitatively relating measured impedance spectra to underlying microstructural features remains an open modeling challenge. We present a two-component framework that combines microstructure generation with impedance prediction to predict microstructure-resolved impedance in a Li/Li₆PS₅Cl/Li symmetric cell. Spatially resolved Li₆PS₅Cl microstructures are generated using phase-field sintering simulations, and impedance is computed for each fixed microstructure snapshot using an Ohmic conduction model incorporating Butler-Volmer kinetics and double-layer capacitance at the Li/SE interfaces. Across the sintering sequence, increasing porosity increases impedance, whereas improved inter-particle contact decreases it. When isolating the effects of the solid electrolyte interphase (SEI), we find that grain boundaries have only a minor effect on impedance, while SEI volume fraction and phase conductivity strongly influence the response. A multi-phase SEI significantly increases impedance. Finally, the same pipeline predicts impedance directly from experimental micrographs using AI-assisted pixel extraction, providing a pathway toward quantitative microstructure–impedance correlations based on real SE microstructures.