This work investigated the utility of performing efficiency calibration for environmental gamma spectrometry using the Monte Carlo based, free of charge GATE toolbox. The validity of this approach was tested by comparing output efficiency values of an in-house developed GATE-based program with experimental measurements covering various geometries and primary photon energies. The results of this comparison revealed relative deviations within ±20%, thus validating the employed computational approach. Moreover, the GATE-based method was able to predict quantities that are generally difficult to measure experimentally, such as the number of interactions preceding full energy absorption. These computationally obtained predictions were found to be in agreement with theory.