Bi2Te3 has recently received considerable attention because of its various characteristics and applications potential. The effort to incorporate dopants into Bi2Te3 to achieve particular features has continued. We investigated Bi-rich Bi2Te3 nanobelts, which were synthesized by the VLS method. We confirmed that single crystalline Bi-rich Bi2Te3 nanobelts with 1:1 of Bi:Te atomic ratio had a hexagonal Bi2Te3 crystal structural phase, using X-ray diffraction and scanning transmission electron microscopy. The results from electrical and magneto-transport measurements of a Bi-rich Bi2Te3 nanodevice revealed three different transition regions, in which different magnetoresistance behaviors were observed, and where the maximum magnetoresistanee ratio was about 105%. These characteristics could provide a wider perspective for potential of Bi-rich Bi2Te3 nanodevices.