In the present work, for the first time, the electrical–thermal conductivity of a composite random material is correlated with the number of conductive paths, the mean path length, and the mean effective path width measured in a representative surface element (RSE) by Monte Carlo sampling. This work is organized in two parts. The theoretical calculation takes place in the first part for the correlation of conductive paths by adopting three approaches (incremental with respect to accuracy and complexity) based on: (i) one-component straight paths; (ii) one-component non-straight paths; (iii) multi-component non-straight paths. In the second part, a novel numerical methodology for the calculation of the conductance of the RSE through the conductive paths, mean path length and the mean effective path is developed for the general model of multi-component non-straight line paths based on Ohm’s law. In addition, a methodology that reduces the calculated conductivity from the microscale to the macroscale is proposed, that takes into account the probability of percolation for finite sizes and the average value of the conductivity from the samples in which percolation occurs. After the necessary consistency steps and verification of the method and its implementation on random binary material systems, it is further applied to solve synthetic continuous percolation problems at the microscale and macroscale. The results and the accuracy of the calculations are in close agreement with existing models. The electrical Direct Current (DC) and thermal conductivity follow the same scaling relation and the proposed methodology can be applied at the same stage without additional cost. In a random binary medium the simulations showed that a scaling law of conductivity is followed by an exponent value close to 1.3. In addition, the number of conductive paths, the average length of the paths, and the effective width follow scaling laws with exponents 1.44±0.01 , −0.25±0.01 and −0.39±0.01, respectively.