ZIF-derivatized catalysts have shown high potential in catalysis. Herein, bean sprout-like Co-TiO2/Ti nanostructures were first synthesized by thermal treatment at 800 °C under Ar-flow conditions using sacrificial ZIF-67 templated on Ti sheets. It was observed that ZIF-67 on Ti sheets started to thermally decompose at around 350 °C and was converted to the cubic phase Co3O4. The head of the bean sprout structure was observed to be Co3O4, while the stem showed a crystal structure of rutile TiO2 grown from the metallic Ti support. Cu sputter-deposited Co-TiO2/Ti nanostructures were also prepared for photocatalytic and electrocatalytic CO2 reduction performances, as well as electrochemical oxygen reaction (OER). Gas chromatography results after photocatalytic CO2 reduction showed that CH3OH, CO and CH4 were produced as major products with the highest MeOH selectivity of 64% and minor C2 compounds of C2H2, C2H4 and C2H6. For electrocatalytic CO2 reduction, CO, CH4 and C2H4 were meaningfully detected, but H2 was dominantly produced. The amounts were observed to be dependent on the Cu deposition amount. Electrochemical OER performances in 0.1 M KOH electrolyte exhibited onset overpotentials of 330–430 mV (vs. RHE) and Tafel slopes of 117–134 mV/dec that were dependent on Cu-loading thickness. The present unique results provide useful information for synthesis of bean sprout-like Co-TiO2/Ti hybrid nanostructures and their applications to CO2 reduction and electrochemical water splitting in energy and environmental fields.