It remains a challenge to fabricate sacrificial films that are stable in most of solvents and can be readily decomposed on demand. Here we report the fabrication of a near-infrared (NIR) light decomposable sacrificial film by layer-by layer (LbL) assembly of UV-light-decomposable poly((4-(2-bromoethoxy)-5-methoxy-2-nitrobenzyl acrylate) triethylammonium bromide) (PNBA-TEA), poly(sodium 4-styrene-sulfonate) (PSS), branched polyethyleimine (bPEI), and lanthanide-doped upconversion nanoparticles (UCNPs). The RPNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films are stable in deposition solutions of various materials and decompose upon MR light irradiation. In the [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films, UCNPs can convert MR light into UV light, which can decompose PNBA-TEA. After immersing the NIR light-irradiated [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films in 0.1 M aqueous NaHCO3 solution, the disintegration of the entire films occurs because of the repulsive force between the negatively charged photoproduct of PNBA-TEA and PSS. LbL-assembled (PAH/PAA)*50 films deposited on top of the MR-light-decomposable RPNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films can be conveniently released to produce large-area and defect-free (PAH/PAA)*50 free-standing films after NIR light irradiation and subsequent immersion in 0.1 M aqueous NaHCO3 solution. Because of the satisfactory stability and on-demand decomposable property, the [(PNBA-TEA/PSS)*2/(bPEI/UCNPs)*3]*2 films are promising as sacrificial layers for the fabrication of various free-standing films.