This study investigates the use of Brewers’ Spent Grains (BSGs) as a sustainable biocomposite building materials, using cornstarch as a biopolymer binder. BSG aggregates are compared with hemp shives, a conventional aggregate known for its thermal properties. Starch is employed as a natural binder in three different formulations to further reduce the carbon footprint of the building material. Considering aggregates, the first formulation contains only BSGs, the second consists of half BSGs and half hemp shives, and the third uses only hemp shives. In addition, morphological analysis using Scanning Electron Microscopy (SEM) is conducted to examine the microstructure and porosity of the raw BSG and hemp shives. Hygrothermal properties are measured using Heat Flow Meter (HFM) and Dynamic Vapor Sorption (DVS) techniques, while mechanical properties are also assessed. Results indicate that the thermal conductivity of the BSG formulation (0.131 W/(m·K)) is double that of the hemp shives formulation (0.067 W/(m·K)), whereas the mixed BSG/hemp shives formulation exhibits a thermal conductivity of 0.106 W/(m·K). However, DVS measurements reveal better hygrothermal properties for the BSG formulation compared to the hemp shives formulation. Lastly, mechanical properties are found to be nearly equivalent across the three formulations. These findings suggest that BSG waste has potential as a viable material for use in construction. Further work on formulation optimization and durability is necessary to fully realize the potential of this waste in promoting a circular economy within the building materials industry.