Robust and facile strategies are required to fabricate film with high luminescence for application in the fields of biomaterials. In this study, the luminescent electrospinning cellulose fibrous mats were decorated with CdTe quantum dots (QDs) and poly(-diallyl dimethyl ammonium chloride) (PDDA) using layer by layer (LBL). The characterizations of the LBL films coated mats were executed by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy, fluorescent spectroscopy, X-ray diffraction, thermal gravimetric analysis, and differential scanning calorimetry. The luminescent intensities were linearly increased with adding the amount of deposited bilayers. The green fabricated (QDs/PDDA) n coated mat through physical interactions is a promising luminescent material.