A simple Monte Carlo model has been developed for calculating the structural features and properties of low molecular weight triols produced by the base-catalyzed propoxylation of glycerin. The model computes the probability of a reaction to a specific oligomer from the local site reactivities of model compounds with an adjustment for the molecular weight of the reacting oligomer. The resulting product array is then used to calculate typical polymer properties such as average molecular weight, polydispersity, and average chain length. Trial rate constants were estimated from the activation energies of MNDO-PM3 semi-empirical molecular orbital theory. For the compounds used to model the oligomer chain end groups, the activation enthalpies were found to be within the ranges reported for experimental values. Although the predicted enthalpies of activation were significantly higher for the alkoxylation directly at glycerin, this was found to be attributable to intramolecular hydrogen bonding in the reactants that was disrupted in the transition states. Although the hydrogen bonding energies were higher than what are normally considered typical, comparison tests showed that the calculated energies agreed well with experimental values of alkoxide anion-alcohol systems. The PM3 rate constants, when used to calculate Monte Carlo probabilities, predicted the isomer distribution of the four isomeric monopropoxylates with a error of 4%. Optimization of the model reduced this to 0.5%. However, to accurately predict the oligomer distribution of higher molecular weight adducts and other properties, the correction term (M(o)/M(i))b had to be included, where M(o)/M(i) is the ratio of the molecular weight of glycerin to the molecular weight of the oligomer undergoing alkoxylation, and b is assigned the value 0.7. Although b is empirical, it is consistent with a simple molecular mechanics (MM2) conformational study of the relative availability of the reactive end groups. When the final model was used to simulate the propoxylation of glycerin for a variety of PO/glycerin ratios, it was found to accurately reproduce properties such as primary hydroxyl content, polydispersity, oligomer distribution, and change in the monopropoxylate isomer ratio as a function of bulk PO/glycerin ratio.