The development of the next generation of advanced lithium-ion batteries (LIBs) requires new & advanced materials and novel fabrication techniques in order to push the boundaries of performance and open up new and exciting markets. Structured carbon materials, with controlled pore features on the micron and nanometer scales, are explored as advanced alternatives to conventional graphite as the active material of the LIB anode. Mesoporous carbon materials, carbon nanotube-based materials, and graphene-based materials have been extensively investigated and reviewed. Morphology control (e.g., colloids, thin films, nanofibrous mats, monoliths) and hierarchical pores (particularly the presence of large pores) exhibit an increasing influence on LIB performance. This tutorial review focuses on the synthetic techniques for preparation of porous carbon spheres and carbon monoliths, including hydrothermal carbonization, emulsion templating, ice templating and new developments in making porous carbons from sustainable biomass and metal–organic framework templating. We begin with a brief introduction to LIBs, defining key parameters and terminology used to assess the performance of anode materials, and then address synthetic techniques for the fabrication of carbon spheres & monoliths and the relevant composites, followed, respectively, by a review of their performance as LIB anode materials. The review is completed with a prospective view on the possible direction of future research in this field.