Process engineering applications such as heat transfer, reactions, and separations involve passing fluid through a porous medium. Historically, random-channel porous media have been used for these operations. Such systems do not represent optimal configurations for process performance because of poor flow distribution and highpressure drop. It is now possible to fabricate porous monoliths with tailored morphology and regular channel structure using 3D-printing. In this work, we use magnetic resonance imaging to study flow through a Schwarz Diamond triply periodic minimal surface (TPMS) monolith for Reynolds numbers up to 350. A transition to unsteady flow was observed experimentally for the first time. The channel structure diverts flow such that free shear layers form in the channel centers that contribute to flow instability. These measurements serve to inform the design of novel transport processes with enhanced performance.