A coral-like film of nickel@nickel sulfide (Ni@NiS) was obtained on a conducting glass through an electrochemical method, in which the Ni functioned as a template. Three types of Ni thin films were electrodeposited on fluorine-doped tin oxide (FTO) substrates by a pulse current technique at the passed charge densities of 100, 200, and 300 mC cm⁻², which rendered custard apple-like, coral-like, and cracked nanostructures, respectively. Subsequently, nickel sulfide films were coated on these Ni films by using a pulse potential technique. Due to the template effect of the Ni films, the composite films of Ni@NiS also assumed the same structures as those of their nickel templates. In each case of the films the particle of the film assumed a core–shell structure. The Ni@NiS coated FTO glasses were used as the counter electrodes for dye-sensitized solar cells (DSSCs). The DSSC with the coral-like Ni@NiS film on its counter electrode exhibits the highest power conversion efficiency (η) of 7.84%, while the DSSC with platinum film on its counter electrode shows an η of 8.11%. The coral-like Ni@NiS film exhibits multiple functions, i.e., large surface area, high conductivity, and great electrocatalytic ability for iodine/triiodine (I⁻/I₃⁻) reduction. X-ray photoelectron spectroscopy (XPS), X-ray diffraction pattern (XRD), scanning electron microscopy (SEM), and four-point probe technique were used to characterize the films. The photovoltaic parameters are substantiated using incident photon-to-current conversion efficiency (IPCE) curves, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Tafel polarization plots. The IPCE curves were further used to calculate theoretical short-current densities of the cells.