Accurate ab-inito quantum mechanical calculations of pyrrole dimers are reported. The thermodynamical stabilities of dimers with alpha - alpha, alpha -beta, and beta - beta type linkages are compared in order to predict the possibilities of branching in polypyrroles. Calculations employing large basis sets and including electron correlation effects predict the alpha -alpha dimers as the most stable form. However, an alpha - beta type bonding requires only 1.5-2.0 kcal/mol, and the energy necessary to introduce a beta - beta type bond is 3.6-4.0 kcal/mol. These values show that a high degree of branching is possible even at room temperatures.