Self-assembly has long being used to control covalent and non-covalent interactions where molecular design has been the major driving force to achieve a desired outcome. Like in nature, a full control over self-assembly processes could lead to rationalized structure-property correlations, a long-time sought in chemistry, physics and materials science. However, the pathways followed and the mechanisms underlying the formation of supramolecular aggregates are still largely unknown and unresolved. Accordingly, the elucidation of nucleation and growth mechanisms will be highly required to push supramolecular chemistry to the next level, where access to nature inspired functions will be accomplished. In this contribution, I will present how reaction-diffusion (RD) conditions established within microfluidic devices can be used to uncover pathway complexity as well as to trigger pathway selection. Specifically, I will show that microfluidic RD conditions provide an unprecedented kinetic control over self-assembly processes; for example, enabling the isolation of well-defined kinetically trapped states as well as unprecedented metastable intermediates. This research provides a new tool to study and understand supramolecular chemistry, and opens up new avenues for the engineering of advanced functional materials and assemblies.