Cobblestone-like CoSb3 nanoparticle films have been achieved via a catalyst-free vapor transport growth technique. The thermoelectric properties of the nanoparticle films were measured from room temperature to around 500 oC. The resultant CoSb3 nanoparticle films show high electrical conductivities due to clean particle surfaces. A maximum power factor reaches 1.848×10−4 W/mK2 at 440 oC. The discussed approach is promising for realizing new types of highly efficient thermoelectric semiconductors.