The highly conductive and flexible nickel-polyethylene terephthalate (Ni-PET) substrate was prepared by a facile way including electrodeposition and hot-press transferring. The effectiveness was demonstrated in the counter electrode of dye-sensitized solar cells (DSSCs). The Ni film electrodeposition mechanism, microstructure, and DSSC performance for the Ni-PET flexible substrate were investigated. The uniform and continuous Ni film was first fabricated by electroplating metallic Ni on fluorine-doped tin oxide (FTO) and then intactly transferred onto PET via hot-pressing using Surlyn as the joint adhesive. The obtained flexible Ni-PET substrate shows low sheet resistance of 0.18Ω/□ and good chemical stability for the I(-)/I(3-) electrolyte. A high light-to-electric energy conversion efficiency of 7.89% was demonstrated in DSSCs system based on this flexible electrode substrate due to its high conductivity, which presents an improvement of 10.4% as compared with the general ITO-PEN flexible substrate. This method paves a facile and cost-effective way to manufacture various metals on a plastic nonconducive substrate beneficial for the devices toward flexible and rollable.