Branched nanocrystals (NCs) enable high atomic surface exposure within a crystalline network that provides optimized transport properties. Herein we report on the colloidal synthesis of branched ceria NCs by means of a ligand-mediated overgrowth mechanism. In particular, the differential coverage of oleic acid as X-type ligand at ceria facet with different atomic density, atomic coordination deficiency and oxygen vacancy density, results in a preferential growth in the [111] direction and thus in the formation of ceria octapods. Alcohols, through and esterification alcoholysis reaction, promote faster growth rates that translate into nanostructures with higher geometrical complexity, increasing the branch aspect ratio and triggering the formation of side branches. The presence of water on the other hand resulted in a significant reduction of the growth rate, decreasing the reaction yield and eliminating side branching, which we associate to a displacement of the alcoholysis reaction. Overall, adjusting the amounts of each chemical, well-defined branched ceria NCs with tuned number, thickness and length of the branches and with overall size ranging from 5 to 45 nm could be produced. We further demonstrate such branched ceria NCs to provide higher surface areas and related oxygen storage capacities (OSC) than quasi-spherical NCs obtained in the presence of only oleylamine.