International audienceWe describe here a new, easy and scalable route for synthesising colusites by using mechanical-alloying and reactive spark plasma sintering, together with the thermoelectric behaviour of zinc-substituted derivatives, Cu26-xZnxV2Sn6S32 (0 ≤ x ≤ 2). X-ray diffraction analysis coupled with transmission electron microscopy evidences the high crystallinity of the as-synthesized samples. In the pristine compound, an intrinsic exsolution phenomenon leads to the formation of two distinguishable colusite phases. Additional neutron powder diffraction results support the substitution of Zn in the tetrahedral Cu sites and 119Sn Mössbauer spectroscopy analyses prove the presence of only Sn4+ in colusite irrespective of the Zn conte...