Abstract Free standing, binder free, and conductive additive free mesoporous titanium dioxide/carbon hybrid electrodes were prepared from co‐assembly of a poly(isoprene)‐block‐poly(styrene)‐block‐poly(ethylene oxide) block copolymer and a titanium alkoxide. By tailoring an optimized morphology, we prepared macroscopic mechanically stable 300 μm thick monoliths that were directly employed as lithium‐ion battery electrodes. High areal mass loading of up to 26.4 mg cm−2 and a high bulk density of 0.88 g cm−3 were obtained. This resulted in a highly increased volumetric capacity of 155 mAh cm−3, compared to cast thin film electrodes. Further, the areal capacity of 4.5 mAh cm−2 represented a 9‐fold increase compared to conventionally cast electrodes. These attractive performance metrics are related to the superior electrolyte transport and shortened diffusion lengths provided by the interconnected mesoporous nature of the monolith material, assuring superior rate handling, even at high cycling rates.