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Thermoelectric materials can convert heat energy into electrical energy. Thermoelectric uses three effects were Seebeck, Peltier, and Thomson effects. Good thermoelectric materials exhibit a large Seebeck coefficient, high electrical conductivity, and low thermal conductivity so that the material might show a good figure of merit (ZT) coefficient. A series of Co4Sb12 skutterudites compound shows excellent potential as a thermoelectric material because Sb-based skutterudites thermoelectric materials possess high mobility, large atomic mass, low electrical resistivity, and Seebeck coefficient reaches up to 200 µV/K. So far the compound was synthesized based on interstitial doping. In this paper, we report on the study preparing of Co4Sb12 skutterudites for which introducing transition metal atom (Ni) ion at Co site to modify a local distortion which in turns to increase of ZT value. Co4Sb12 skutterudites were synthesized using the modified polyol method and fabricated into thin films on glass substrates. Before fabrication, Co4Sb12 skutterudites was dissolved into DMF. The fabricated Co4-xNixSb12 skutterudites films were characterized using XRD, SEM-EDX, UV-VIS, and I-V meter to determine the structure and thermoelectric properties of Co4-xNixSb12 skutterudites. It is found that the crystal system of obtained Co4-xNixSb12 skutterudites falls to cubic with the space group of Im-3 (204). Further analyses of XRD data also shows that the crystallinities are 7.65 and 9.35%, for samples respectively for x = 0 and 0.1. The phase purity of the Co4-xNixSb12 samples reach up to 74, and 63% for x = 0 and 0.1 respectively. The result of UV-VIS spectra analyses shows the band gap for samples x = 0 and 0.1 were 2.59 and 2.66 eV, which indicates the samples are semiconductors like which lower than semiconducting oxides. The I-V meter result shows that the increased electrical conductivity with increasing temperature, indicating that the samples can be used as a raw material for the thermoelectric device. Besides that, the values of electrical conductivity for samples reach 10-4 Ω-1. cm-1, which also indicates the samples were semiconductors.