Origin of life research can be coarsely categorized into opposing two principles, sometimes called heterotrophic and autorophic origins. Autotrophic origin assumes that life started with a sparse chemical system that later evolved into the biochemical network, whereas heterotrophic origin follows the transformation of the initial complex chemical system. The fact that many experiments modeling prebiotically plausible conditions result in complex “messy” systems — a diverse, dynamic array of small molecule and polymeric products formed by a wide range of chemical processes — supports the idea of heterotophic origin. The principles of selectivity and organization in these messy systems are not well understood, as the mixtures present an analytical challenge. Herein we offer a study of the selective synthesis of hyperbranched polyesters undergoing wetting-drying cycles, a simplified model messy chemical system.