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Type-I clathrates have been considered as very promising thermoelectric (TE) materials thus attracting attention widely. Here we report new clathrates Ba8CuxSiyGe46-x-y (4≤ x ≤ 6.5, y = 0 and 5.15 ≤ x ≤ 6.425, 2.05≤ y ≤ 36.9), focusing on their phase purity and TE properties. Our results show that samples prepared by arc melting followed by annealing are multi-phases alloys. The composition of the clathrate phase is also inhomogeneous. This indicates that the kinetic factor dominates the reaction of forming the clathrate phase during element-melting and sample-annealing. We select three compositions in these two series of samples, which have less impurity and better composition homogeneity for the clathrate phase, and the annealed alloys are furthered processed by ball milling (BM) and powder-solidification (either by hot pressing (HP) or by spark plasma sintering (SPS)) for TE properties investigations. The BM and HP/SPS processes can improve the phase purity and homogeneity. The TE measurements show that the Si-substituted samples have better performance than the Ge-based sample, mainly by decreasing the electrical resistivity. This indicates that the elemental substitution may be still an effective way to improve the TE performance of clathrates.