LiCoO2 (LCO) thin films are epitaxially grown on (100), (110) and (111) 0.5 wt% Nb-doped SrTiO3 (Nb:STO) substrates by pulsed laser deposition and their crystalline orientation relationship investigated via X-ray pole figure measurement. This investigation reveals that the LCO films grown on Nb:STO (100) and (110) have a cube-on-cube orientation relationship with the substrates to be (104)- and (018)-oriented, respectively, while the relationship is accompanied with 60° in-plane rotation on (111) Nb:STO to yield a predominantly (001)-oriented LCO film. The (104)-oriented LCO film on (100) Nb:STO substrate exhibits high rate capability up to 100 C.