New Ln x Sb 2−x Se 3 (Ln: Yb 3+ , Er 3 ) based nanomaterials were synthesized by a co-reduction method. Powder XRD patterns indicate that the Ln x Sb 2−x Se 3 crystals (Ln=Yb 3+ , Er 3+ , x=0.00–0.12) are isostructural with Sb 2 Se 3 . The cell parameters b and c decrease for Ln=Er 3+ and Yb 3+ upon increasing the dopant content (x), while a increases. SEM images show that doping of the lanthanide ions in the lattice of Sb 2 Se 3 generally results in nanoflowers. UV–vis absorption and emission spectroscopy reveals mainly electronic transitions of the Ln 3+ ions in case of Yb 3+ doped nanomaterials. Emission spectra of doped materials, in addition to the characteristic red emission peaks of Sb 2 Se 3 , show additional emission bands centered at 955nm, originating from the 2 F 7/2 → 2 F 5/2 transition (f–f transitions) of the Yb 3+ ions. DSC curves indicate that Sb 2 Se 3 has the highest thermal stability. The temperature dependence of the electrical resistivity of doped-Sb 2 Se 3 with Yb 3+ and Er 3+ was studied.