An efficient optimization approach is described to calibrate load factors used for designing of structures. The load factors are calibrated so that the structural reliability index is as close as possible to a target reliability value. The optimization procedure is applied to find optimal load factors for designing of structures in accordance with the new version of the Mexico City Building Code (RCDF). For this aim, the combination of factors corresponding to dead load plus live load is considered. The optimal combination is based on a parametric numerical analysis of several reinforced concrete elements, which are designed using different load factor values. The Monte Carlo simulation technique is used. The formulation is applied to different failure modes: flexure, shear, torsion, and compression plus bending of short and slender reinforced concrete elements. Finally, the structural reliability corresponding to the optimal load combination proposed here is compared with that corresponding to the load combination recommended by the current Mexico City Building Code.