Lightweight B4C/Al composites were produced from powders of boron carbide and aluminum by self-propagating high-temperature synthesis (SHS). The effects of postdensification heat treatment at different temperatures and environmental conditions on phase transformations and properties evolution were studied. Heat treatment processing that followed the synthesis was applied using low heating rate in temperature range from 400°C up to 1500°C. An interconnected multiphase (B4C, Al3BC, and c-BN) microstructure was produced in composite as a result of heat treatment at temperatures below 1080°C. The formation of hard and brittle reaction products (AlN, AlB2, Al4C3, and Al8B4C7) at temperatures above 1150°C causes decrease in bending strength and increase in resistance to unlubricated sliding wear.