In this short review, we overview some advancements made in Li-ion battery anode development, where the structural arrangement of the material plays an important role. Specifically, we summarise the benefits of 3D macroporous structure imposed the anode material, in order to improve ionic and electronic conductivity in the absence of conductive additives and binders. Two anode materials are overviewed: TiO2 and GeO2. These are either high capacity anode materials or accessible, abundant materials that are capable of very stable and long-term cycling. We have focused this review on 3D inverse opal structures of these anodes and summarise their enhanced behaviour by comparing their performance metrics to a range of nanoscale and porous analogues of these materials.