The highly modular Ugi four-component reaction (Ugi-4CR) was used to directly obtain polymers of high molar mass bearing aromatic residues in the backbone. By using at least two bifunctional monomers, the Ugi-4CR can be employed to synthesize polymers through a polycondensation under mild conditions in the absence of catalysts. This highly versatile approach allows the creation of vast libraries of molecules by a comparably small pool of compounds. We investigated the six different possible types of the Ugi four-component polymerization (Ugi-4CP) to generate polyamides using commercially available monomers without further purification. After substantial adjustments of reaction parameters, we were able to obtain a polymer of high molar mass, albeit only for one out of the six types of the Ugi-4CP. (c) 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1680-1686