Al 2 O 3 :Cr 3+ samples were synthesized via hydrothermal and microwave solvothermal methods and thermal decomposition of Cr 3+ doped precursors. The sample characterizations were carried out by means of X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence (PL) spectra and decay curves. XRD results indicated that Cr 3+ doped samples were pure α-Al 2 O 3 phase after being calcined at 1573K. SEM results showed that the length and diameter of these Cr 3+ doped alumina microfibers by hydrothermal route were about 2–5μm and 100–300nm, respectively; the obtained α-Al 2 O 3 based powders via the microwave solvothermal method were microspheres with an average diameter about 1–2μm. PL spectra showed that the Al 2 O 3 :Cr 3+ samples presented a broad R band at 696nm. It is shown that the 0.3mol% of doping concentration of Cr 3+ ions in α-Al 2 O 3 :Cr 3+ is optimum. According to Dexter's theory, the critical distance between Cr 3+ ions for energy transfer was determined to be 24Å. It is found that the curve followed the single-exponential decay. Furthermore, the luminescence properties of the samples are also dependent on the morphology.