Radon is one of the 19 carcinogenic substances identified by the World Health Organization, posing a significant threat to human health and the environment. Properly removing radon under ambient conditions remains challenging. Compared with traditional radon−adsorbent materials such as activated carbon and zeolite, metal−organic framework (MOF) materials provide a high specific surface area, rich structure, and designability. However, MOF material powders demonstrate complications regarding practical use, such as easy accumulation, deactivation, and difficult recovery. Ni−MOF−74 was in situ grown on a porous polyacrylic acid (PA) spherical substrate via stepwise negative pressure impregnation. Ni−MOF−74 was structured as one−dimensional rod−shaped crystals (200−300 nm) in large−pore PA microspheres, whose porous structure increased the diffusion of radon gas. The radon adsorption coefficient of a Ni−MOF−74@PA−polyethyleneimine composite material was 0.49 L/g (293 K, relative humidity of 20%, air carrier). In comparison with pristine Ni−MOF−74 powder, our composite material exhibited enhanced adsorption and longer penetration time. The radon adsorption coefficient of the composite material was found to be from one to two orders of magnitude higher than that of zeolite and silica gel. The proposed material can be used for radon adsorption while overcoming the formation problem of MOF powders. Our preparation approach can provide a reference for the composite process of MOFs and polymers.