The validity of using the Lucas-Washburn (LW) equation for porous media characterization by the two-liquid capillary penetration method was tested numerically and experimentally. A cylindrical capillary of known radius and contact angle was used as a model system for the tests. It was found that using the LW equation (i.e., ignoring inertia and dynamic contact angle effects) may lead to very erroneous assessment of the capillary radius and the equilibrium contact angle, for a relatively wide range of capillary radii and equilibrium contact angles. A correct assessment requires the application of a penetration kinetics equation that considers inertia and the dynamic contact angle.