Polycrystalline K-filled CoSb3 are synthesized successfully. The uplimit for K filling is at least 0.45, being higher than those of either alkaline-earth (AE) or rare-earth (RE) metals but being in consistent with our earlier theoretical prediction. The measured transport properties (300–800 K) show that K filling does not lower thermal conductivity much in comparison with AE or RE filling due to the relatively low mass of K atom. However, it improves electrical conductivity, retains large Seebeck coefficient, and leads to a reasonably good thermoelectric performance for the filled skutterudites. The maximum figure of merit ZT reaches 1 at 800 K for K0.38Co4Sb12.