Collection efficiency is an important quantity in dosimetry with ionization chambers. It can be calculated by solving a hyperbolic system of partial differential equations. This system can be solved only in few, simple, idealized geometries, but for more realistic designs an analytical resolution is no longer possible. In the present work a Monte Carlo scheme that could permit to calculate the collection efficiency for any ionization chamber geometry is proposed. This scheme has been tested against Boag's approach for three chambers with plane-parallel, cylindrical and spherical geometries, operated in the recombination regime. The results obtained in the full Monte Carlo simulation closely agree with the Boag's ones for the three ideal geometries considered. The largest relative difference, ∼0.3%, has been found for the plane-parallel chamber in case of 50 V, the lowest potential difference investigated in this study. Results appear to be stable against changes in the chamber volume, the ion mobility and the recombination constant. The method proposed could be a useful tool to calculate collection efficiencies of ionization chambers, provided the electric field inside them is known.