Three dimensional hierarchical nanostructures have attracted great attention for electrochemical energy storage applications. In this work, self-supported TiO2@Ni(OH)2 core-shell nanowire arrays are prepared on carbon fiber paper via the combination of hydrothermal synthesis and chemical bath deposition. In this core-shell hybrid, the morphology and wall size of the interconnected nanoflake shell of Ni(OH)2 can be tuned through adjusting the concentration of ammonia solution. Heterogeneous nucleation and subsequent oriented crystal growth are identified to be the synthesis mechanism affecting the nanostructure of the shell material, which consequently determines the electrochemical performance in both energy storage and charge transfer. Superior capabilities of 264 mAh g(-1) at 1 A g(-1) and 178 mAh g(-1) at 10 A g(-1) are achieved with the core-shell hybrids of the optimized structure. The asymmetric supercapacitor prototype, comprising of TiO2@Ni(OH)2 as the anode and mesoporous carbons (MCs) as the cathode, is shown to exhibit superior electrochemical performance with high energy and power densities. The present work provides a clear illustration of the structure-property relationship in nanocrystal synthesis and offers a potential strategy to enhance the battery type Ni(OH)2 electrode in a hybrid supercapacitor device.