To simplify preparation process of AlN/C composite foam, AlN nanomaterials are prepared via double decomposition reaction and then 800℃ annealing process to recrystallize hexagonal AlN (h-AlN) nanowires on carbon foam substrate. Fore the morphology characterization it follows that, h-AlN nanowires with straight cylindrical morphology grow along the [001]direction on carbon microspheres surface and are about 50 nm in diameter and several micrometers in length. Meanwhile, the growth mechanism of nanowire is interpreted as vapor-liquid-solid(VLS) process. The photoluminescence(PL) spectrum of as-prepared sample also researched, and the results show that a sharp photoluminescence peak appears at 423 nm and shifts toward the red side with temperature increasing. The peak is attributed to the transition luminescence, owing to the substitution of C for N impurity energy level. The sample has good PL character in purple light band and is potential to be used the in photodetector field.