The first results of an off-lattice Monte Carlo simulation of network formation by chain polymerization of divinyl liquid-crystalline monomer are presented. Snapshots show the spatial inhomogeneity typical of chain reaction processes. In the present simulations the order in the nematic and smectic B phases decreases only slowly during polymerization. Due to the limited number of particles in the simulation, the radical concentation is necessarily higher than in most experiments. This explains the small number of trapped radicals and the slow increase of the cross-link fraction as a function of conversion. The cross-link, fraction is constant in the moderate-conversion region, in qualitative agreement with experiment.