In the field of 3-D resolved computational modelling of Lithium-ion battery electrodes, the arrangement and properties of the Carbon-Binder-Domain (CBD) play a critical role in the ion and electron transport properties through their impact on the electrode tortuosity factor. However, until now, the CBD porosity value -its main descriptor in terms of transport properties and occupied volume- has been determined through educated guesses due to the lack of an experimental approach. Here, a novel methodology is reported for the determination of the CBD internal porosity through the combination of computational modelling and experimental electrochemical impedance spectroscopy (EIS). The methodology is based on the creation of a calibration curve that relates tortuosity factor with CBD porosity through digital stochastic generation of electrode microstructures and diffusivity characterization. The curve is then compared to the EIS experimental results and analyzed through a transmission line model, yielding a good estimation of the parameters. In this work, the usefulness and the identified limitation of this approach are demonstrated using three different formulations of LiNi0.3Mn0.3Co0.3O2 (NMC 111) cathodes. To the best of the authors’ knowledge, this is the first reported method for estimating CBD porosity.