An accurate assessment of liquid-phase mass transport resistances is necessary for understanding and optimizing battery performance using mathematical models. This work combines modeling and experiments to quantify tortuosity in electrolyte-filled porous battery structures (separator and active-material film). Tortuosities of separators were measured by two methods, AC impedance and polarization-interrupt, which produced consistent results. We measured an apparent interfacial resistance at the lithium metal electrodes that contributed to both ohmic and diffusional resistance of the cell. The polarization-interrupt experiment was used similarly to measure effective electrolyte transport in porous films of cathode materials, particularly films containing LiFePO4. An empirical relationship between porosity and the tortuosity of the porous structures was developed. Our results demonstrate that the tortuosity-dependent mass transport resistance in porous separators and electrodes is significantly higher than that predicted by the oft-used Bruggeman relationship.