Nano-TiO2/CNT/ZrO2 complex film was prepared by sol-gel process, on the nanoTiO2/CNT/ZrO2 composite film electrode, electrocatalytic reduction of 2-pyridinaldehyde in the ionic liquid electrolyte of 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMI]BF4) was studied by cyclic voltammetry and bulk electrolysis. The results showed that the composite film had a porous mesh structure, TiO2 and ZrO2 particles were about 20 nm, which were loaded on carbon nanotubes (CNT) with the diameter of about 40~60 nm, the catalytic performance of nano-TiO2 modified by ZrO2 and CNT was greatly improved. In the indirect electroreduction of 2-pyridinaldehyde to 2-piperidinemethanol by Ti(IV)/Ti(III) redox system on nanoTiO2/CNT/ZrO2 complex film surface in [EMI]BF4, the yield and current efficiency were approximately 83% and 85.6% at -1.40 V, respectively. The electrode reaction mechanism was the called catalytic mechanism.