Metal-organic frameworks (MOFs) have great potential for the development of fire barriers for flammable materials. Accordingly, zirconium-based metal-organic framework (Zr-MOF), branched polyethyleneimine (BPEI), and vinyltriethoxysilane (VTES) were deposited to produce composites assembled on cellulosic fibers to investigate their barrier effects. The structure, morphology, and thermal properties of the cellulosic fibers were characterized using FTIR spectroscopy, SEM, and TGA. Compared with the untreated cotton sample, the temperature of the maximum rate of weight loss (Tmax) of C-Zr-MOF/BPEI/VTES increased from 479 to 523.3 °C and the maximum weight loss rate (Rmax) at Tmax decreased from 37.6 to 17.2 wt%/min. At 800 °C, the pristine cotton was burned out without residues whereas the residual char content of the C-Zr-MOF/BPEI/VTES sample was 7.2355 wt%. From the vertical burning tests, the results suggested that the C-Zr-MOF/BPEI/VTES sample had better barrier effects by reducing the flame-spread speed and generating more protective char layers.