The main issue in this work is to study the limit functions necessary for the reliability assessment of structural steel with the use of the relative entropy apparatus. This will be done using a few different mathematical theories relevant to this relative entropy, namely those proposed by Bhattacharyya, Kullback–Leibler, Jeffreys, and Hellinger. Probabilistic analysis in the presence of uncertainty in material characteristics will be delivered using three different numerical strategies—Monte Carlo simulation, the stochastic perturbation method, as well as the semi-analytical approach. All of these methods are based on the weighted least squares method approximations of the structural response functions versus the given uncertainty source, and they allow efficient determination of the first two probabilistic moments of the structural responses including stresses, displacements, and strains. The entire computational implementation will be delivered using the finite element method system ABAQUS and computer algebra program MAPLE, where relative entropies, as well as polynomial response functions, will be determined. This study demonstrates that the relative entropies may be efficiently used in reliability assessment close to the widely engaged first-order reliability method (FORM). The relative entropy concept enables us to study the probabilistic distance of any two distributions, so that structural resistance and extreme effort in elastoplastic behavior need not be restricted to Gaussian distributions.