We demonstrate a method for tailoring local mechanical properties near channel surfaces of vascular structural polymers in order to achieve high structural performance in microvascular systems. While synthetic vascularized materials have been created by a variety of manufacturing techniques, unreinforced microchannels act as stress concentrators and lead to the initiation of premature failure. Taking inspiration from biological tissues such as dentin and bone, these mechanical deficiencies can be mitigated by complex hierarchical structural features near to channel surfaces. By employing electrostatic layer-by-layer assembly (ELbL) to deposit films containing halloysite nanotubes onto scaffold surfaces followed by matrix infiltration and scaffold removal, we are able to controllably deposit nanoscale reinforcement onto 200 micron diameter channel surface interiors in microvascular networks. High resolution strain measurements on reinforced networks under load verify that the halloysite reduces strain concentrations and improves mechanical performance.