Liquid Scintillation Counting (LSC) is widely used as a very efficient technique for radioactivity quantification. LSC is a powerful tool applied as much in low level environmental radioactivity monitoring, as in radionuclide metrology for the activity standardization of electron capture, pure-beta, and alpha nuclides. In order to quantify the sample activity, the number of scintillation photons are counted by one or several PMTs. However, the scintillation count rate varies with the detection efficiency. As an alternative to traditional methods for the calculation of detection efficiency, a Monte Carlo approach based on GEANT4 toolkit is presented for the simulation of light emission inside a Quantulus 1220 liquid scintillation counter with two PMT photomultipliers tubes working in sum-coincidence mode. To this end, the GEANT4 simulation handles a variety of processes at optical wavelengths including refraction and reflection at medium boundaries, Rayleigh scattering and bulk absorption, and additional processes which produce optical photons such as Cherenkov effect, transition radiation and scintillation, and includes a description of optical properties associated with each material constituting the detection system. The objective is to simulate the propagation of optical photons from their creation in the liquid scintillation cocktail to the production of photoelectrons in the PMTs. In this paper, we report in detail the results of the proposed simulation (detection efficiency, and additionally wall effect and absorption probabilities of gamma-rays) for different radionuclides such as 14C, 3H, 54Mn and 90Y, and its validation through the comparison with the experimental measurements.