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 001direction 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.