Thermoelectric materials have attracted much attention due to the current interest in energy conversion and recent advancements in nano-engineering. A simple approach to synthesize BiTe and Bi2Te3 micro/nanowires was developed by combining solution chemistry reactions and catalyst-free vapor-solid growth. A pathway to transform the as-grown BiTe nanostructures into Bi2Te3 can be identified through the Bi-Te phase diagram. Structural characterization of these products was identified using standard microscopy practices. Meanwhile, thermoelectric properties of individual Bi-Te compound micro/nanowires were determined by the suspended microdevice technique. This approach provides an applicable route to synthesize advanced high performance thermoelectric materials in quantities and can be used for a wide range of low-dimensional structures.