Porous polymer films that can be employed for broadband and omnidirectional antireflection coatings are successfully shown. These films form a gradient-refractive-index structure and are achieved by spin-coating the solution of a polystyrene-block-poly (methyl methacrylate) (PS-b-PMMA)/PMMA blend onto an octadecyltrichlorosilane (OTS)-modified glass substrate. Thus, a gradient distribution of PMMA domains in the vertical direction of the entire microphase-separated film is obtained. After those PMMA domains are removed, a PS porous structure with an excellent gradient porosity ratio in the vertical direction of the film is formed. Glass substrates coated with such porous polymer film exhibit both broadband and omnidirectional antireflection properties because the refractive index increases gradually from the top to the bottom of the film. An excellent transmittance of >97% for both visible and near-infrared (NIR) light is achieved in these gradient-refractive-index structures. When the incident angle is increased, the total transmittance for three different incident angles is improved dramatically. Meanwhile, the film possesses a color reproduction character in the visible light range.