As Si single-junction technology is approaching its Shockley–Queisser theoretical limit, relevant efforts are being expended towards the development of multi-junction modules. In this work, we employ an optical model based on Monte Carlo ray tracing to compare four different multi-junction modules in a voltage-matched two-terminal (VM2T) configuration. In particular, we took into consideration the VM2T coupling of crystalline silicon cells with CuInxGa1-xSe2 (CIGS), CdTe, GaAs and perovskite (PVK) solar cells. We optimized the thicknesses of each layer in the top sub-module and determined the performance of VM2T modules in the Shockley–Queisser theoretical limit. We also considered the possibility of using modules in which the top Si surface is flat to determine the performance drop due to the absence of the texturization on the top Si surface. Moreover, we determined the optimal bandgap energy of PVK in a VM2T PVK/Si module as well as the highest efficiency achievable. Lastly, we show that when using state-of-the-art cells, the highest VM2T efficiency achievable for the considered materials is 34.2% under standard test conditions.