In competitive thermoelectric devices for energy conversion and generation, high-efficiency materials of both ntype and p-type are required. For this, Bi2Te3-based alloys have the best thermoelectric properties in room temperature applications. Partial replacement of tellurium by selenium is expected to introduce new donor states in the band gap, which would alter electrical conductivity and thermopower. We report on the preparation of n-type Bi-2(Te1-xSex)(3) solid solutions by a straightforward arc-melting technique, yielding nanostructured polycrystalline pellets. X-ray and neutron powder diffraction was used to assess Se inclusion, also indicating that the interactions between quintuple layers constituting this material are weakened upon Se doping, while the covalency of intralayer bonds is augmented. Moreover, scanning electron microscopy shows large surfaces perpendicular to the c crystallographic axis assembled as stacked sheets. Grain boundaries related to this 2D nanostructuration affect the thermal conductivity reducing it below 0.8 Wm(-1)K(-1) at room temperature. Furthermore, Se doping increases the absolute Seebeck coefficient up to -140 mu V K-1 at 400 K, which is also beneficial for improved thermoelectric efficiency.