Porous Li4/3Ti5/3O4 (LTO) and LTO/M (M=Ni, Co) composites have been synthesized using a template-free sol-gel procedure. Porosity is simply controlled by varying the metal content. Due to the porous morphology and enhanced electronic conductivity, these materials display a superior electrochemical performance as anode materials in lithium ion batteries. Oxidation of the LTO/M composites in air yields a dispersion of M/MOx nano-(micron-sized) particles that are regularly distributed on a 3D macroporous LTO matrix and exhibit a reversible electrochemical activity with lithium. In this new architecture (LTO/M/MOx), the ratio and composition of M/MOx particles are readily controlled by varying the synthesis/oxidation conditions. The new substrate (porous LTO) participates in capacity, with no change in volume, and overcomes drawbacks of using metallic substrates such as high cost, fragile structure and the low volumetric specific capacity.