The emission spectrum of AlO radicals was analyzed in 440-540 nm in the reaction of laser ablated Al beam and O2. The carrier of spectrum was assigned to Δν=0, ±1, ±2 vibrational sequences of B2Σ+-X2Σ+ transition of AlO radicals, the observed maximum vibrational quantum number was ν′=6. The rotational and vibrational temperatures of B state were estimated at 3000 and 7500 K by spectrally simulating the rovibronic population distribution. There is a strong evidence that the production of excited Al(2S) atoms is essential to the formation of excited AlO radicals.