Recently, there has been a growing interest in skutterudite (SKD) compounds containing electronegative elements such as Br, Cl, S, Se, and Te, owing to their increased diversity and the versatility of filler atoms. This study focused on the thermoelectric performance of a series of (Ni, Te) co-doped SKDs filled with the electronegative element S, denoted as SxNi0.4Co3.6Sb11.2Te0.8 (x = 0, 0.1, 0.2, and 0.3). These compounds were prepared using a combination of a solid-state reaction and spark plasma sintering techniques. The results showed that (Ni, Te) co-doping introduced excess electrons in the SKD lattice, while the incorporation of the element S into the SKD voids optimized carrier concentration. This led to a considerable increase in the absolute Seebeck coefficient to 110.6 μV K−1 at ambient temperatures. The presence of S fillers induced phonon resonance scattering and point scattering, which reduced lattice thermal conductivity and ultimately improved the thermoelectric figure of merit zT, which reached 0.93 for S0.3Ni0.4Co3.6Sb11.2Te0.8 at 823 K.