In this study, an effective method of slow hydrolization of metal alkoxide (e.g., Ti(C4H9O)4) in an ethanol-water system was systematically investigated and used to finely control the deposition of titania on carbon colloids. A model of adsorption-hydrolization of precursors during the coating process was rationally built for the first time to interpret the usability of the method and facilitate its further extension. Using this strategy, titania in the form of supported nanocrystals or layers on carbon colloids (TiO2 shell/C core nanoparticles; C@TiO2) was successfully tailored. Meanwhile, finely dispersed hollow TiO2 nanoparticles with shells consisting of different cryst. structures were also prepd. by varying the calcination conditions after removing the carbon cores. More importantly, the effects of the cryst. and nano/macrostructures of the as-prepd. TiO2 samples in photocatalysis and lithium-ion battery applications were analyzed in detail. The preliminary results show that anatase-rutile T