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A new kind of crosslinkable potato starch-based graft copolymer emulsion (PoSt-g-BMD) has been prepared using butyl acrylate (BA) and methyl methacrylate (MMA) as main monomers, and diacetone acrylamide (DAAM) as functional monomer. The keto-carbonyl group of DAAM in PoSt-g-BMD copolymer could react with adipic dihydrazide (ADH) at ambient temperature to form cross-linked copolymer. The PoSt-g-BMD had been characterized by the FT-IR spectra and thermogravimetric analysis (TGA). It was applied to prepare the humidity-controlling coatings (PoSt-g-BMD-C). The water absorption of PoSt-g-BMD-C was 105%. The humidity controlling properties were also measured, and the PoSt-g-BMD-C exhibited humidity sensitivity and humidity retention because fillers of porous structure combined with PoSt-g-BMD copolymer emulsion based on scanning electron microscopy images (SEM). It could be widely applied in indoor coating for controlling humidity.