Thermoelectric materials are solid state devices having the capability to convert heat to electrical energy and vice versa. These materials are simple, have no moving parts and use no greenhouse gases. But the major drawback of these materials is their low conversion efficiency. Hence enhancement of thermoelectric efficiency is required to make the use of these devices widespread. Thermoelectric efficiency is related to a parameter termed figure of merit, ZT which is associated with the inter-related transport properties such as Seebeck coefficient, electrical and thermal conductivity. Efficient thermoelectric material should possess high Seebeck coefficient (S), high electrical conductivity () and low thermal conductivity (). The present investigation revolves around improvement of ZT of CoSb3 either by chemical doping or through microstructural modifications. These materials possess structural voids, which can be filled with foreign atoms. The rattling motion of these filler atoms reduces the thermal conductivity of these materials, thereby increasing the thermoelectric efficiency. The rattler atoms chosen for the present study are Mn and Yb. Both coarse and fine-grained MnxCo4Sb12 (x = 0. 0.2, 0.4, 0.8, 1.2 and 1.6) and Yb0.19Co4Sb12 have been synthesized and subjected to various structural and functional property characterizations. The structural study based on Rietveld Analysis and the corresponding difference Fourier maps confirms the void occupancy by Mn and Yb in MnxCo4Sb12 (x 0.2, 0.4 and 0.8) and Yb0.19Co4Sb12. In higher Mn content, x=1.2 and 1.6, Mn was found to partially substitute Co site and partially fill the voids and the remaining precipitated out as free particles. A comparative study of coarse and fine-grained CoSb3 has thrown light in to the grain size effect on the thermoelectric properties. Lowering of grain size helped in enhancement of ZT in CoSb3. Seebeck coefficient (thermoelectric power), electrical and thermal conductivity have been measured for different concentrations of the filler Mn atoms between 300K and 673K. A change in sign of the Seebeck coefficient from negative to positive occurs, when Mn concentration exceeds x=0.8. Electrical resistivity values was found to decrease initially with Mn filling with the minimum value at Mn content, x=0.4 and then gradually increase as Mn content increases. The thermal conductivity value decreases with Mn content in the CoSb3 indicating their rattling property which helps in the enhancement of the overall thermoelectric efficiency. There is a reduction in the value of ktotal in Mn filled CoSb3 than that of the unfilled counterpart. This decrease in the ktotal is a clear indication of the rattling motion of the filler Mn atom in the structural void of CoSb3. Highest ZT of 0.36 is achieved by Mn0.4Co4Sb12 at 373K. Higher concentration of Mn (with x= 1.2 and 1.6) proved to be detrimental in terms of improvement of the value of ZT. Grain size reduction helped in improvement of ZT in Mn0.2Co4Sb12. Maximal ZT of 0.06 at 523K is achieved in hot pressed Mn0.2Co4Sb12. The corresponding coarse-grained material is found to possess ZT of 0.01 at the said temperature. The enhancement can be attributed to high / ratio and high density. Similarly, fine grained Yb0.19Co4Sb12 shows higher ZT compared to the coarse-grained sample because high / and high S.