Nanocrystalline mullite has been synthesized by sintering of absorbed monophasic aluminosilicate precursors into cotton wool and filter paper cellulosic structures. Effects of molybdenum and tungsten doping on template mediated mullite at 1200 degrees C and 1400 degrees C have been investigated using differential thermal analysis (DTA), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR) and field emission scanning electron micrographs (FESEM). Microstructures of the sintered samples revealed successful replication of cellulosic structure with the formation of dense mullite phases having grain diameter in the range of 50-80 nm. Strong photoluminescence emissions in the UV and visible regions result from the oxygen vacancies and Al-O bonds present in mullite structures.