The composition modification and structure manipulation of carbon-based battery electrodes is becoming an increasingly urgent need for safer, more reliable, and effective electric vehicles. Herein, we fabricate a free-standing hybrid anatase-bronze TiO2-grafted reduced graphene oxide (TiO2-rGO) through a one-pot solvothermal procedure. The TiO2-rGO composite was transformed into a film with an anisotropic alignment and assembled as an anode into lithium-ion batteries (LIBs) to enhance its performance. Our previously developed “Pulse Freezing” process, with modifications including: (1) dimensional and structural optimization for larger and faster film production and (2) optimal microfluidic condition for vertical porous alignment, is utilized for assembling this nanocomposite anodic film. During the microfluidic assembly process, we achieved the desirable flowrate, flow patterns, and alignments of the integrated TiO2-rGO layers while forming porous microstructures through freeze drying. The porous and aligned TiO2-integrated rGO film exhibits a significantly enhanced specific capacity of 400 mAh/g at 0.2 A/g, which is a drastic increase compared to traditional TiO2 and carbon black electrodes possessing <50 mAh/g capacity, attributed to the anisotropic alignment and porous microstructure of rGO in combination with TiO2 grafting. The developed TiO2-rGO composite film provides a promising application of Ti-based electrodes in LIBs for commercial battery industries.