The double layer of electrode/electrolyte interfaces plays a fundamental role in determining the performance of solid state electrochemical cells. The double layer capacitance is one of the most-studied descriptors of the double layer. This work examines a case study on lanthanum strontium vanadate (LSV)/yttria-stabilized zirconia (YSZ) interfaces exposed in solid oxide fuel cell anode environment. The apparent double layer capacitance is obtained from impedance spectroscopy. The intrinsic double layer capacitance is evaluated based on Stern's method in conjunction with the Volta potential analysis across LSV/YSZ interfaces. Both the apparent and the intrinsic double layer capacitances exhibit right-skewed volcano patterns, when the interfaces are subjected to anodic biases from 0 to 150 mV. The apparent double layer capacitance is about one order of magnitude larger than the intrinsic double layer capacitance. This discrepancy roots in the inconsistent surface areas that are involved. This analysis of capacitance would provide a more realistic TPB estimate of a working solid-state electrochemical device.