In this paper, we investigated the structure and microstructure of In 4 Te 3 nanopowders obtained by mechanically alloying an In 75 Te 25 powder mixture. Structural, chemical, thermal and vibrational studies of the In 75 Te 25 powder mixture were carried out using X-ray diffraction, energy dispersive spectroscopy, transmission electron microscopy, differential scanning calorimetry and Raman spectroscopy. The orthorhombic In 4 Te 3 phase (In 3 Se 4 -type) was nucleated in 2h of synthesis, although non-reacted tetragonal indium (In) was still present at that time. Small amounts of cubic In 2 O 3 phase were observed after 31h of synthesis. Rietveld analyses allowed the measurement of mean crystallites sizes and phase fraction variations when milling times were increased. These analyses showed that, after 31h of synthesis, about 65wt% of In 4 Te 3 phase contained mean crystallite sizes smaller than 27nm and microstrains greater than 1.5%. The crystallite and interfacial components sizes were determined by high resolution transmission electron microscopy. Differential scanning calorimetry measurements showed the influence of nanometric crystallite sizes on the melting of the In 4 Te 3 and non-reacted In phases. Raman measurements showed that the trigonal Te and α-TeO 2 modes, observed for the precursor Te powder, are absent for the sample milled for 31h. The structural stability of the nanocrystalline phases of the In 75 Te 25 sample milled for 31h was attested by X-ray diffraction measurements performed twelve months after its production.