In a purpose to develop good dispersity and compatibility of layered double hydroxide (LDH) in polypropylene (PP) matrix, a novel DOPOi-LDH@GO hybrid nanomaterial was fabricated via three-step reactions including the synthesis of DOPO-itaconic acid (DOPOi), an electrostatic adsorption of LDH coating on the surfaces of graphene oxide (GO) (LDH@GO), and the preparation of DOPOi-LDH@GO by an anion exchange. The thermal stability and crystallization behaviors of PP/DOPOi-LDH@GO nanocomposites are greatly different from neat PP. The thermal stability of PP/DOPOi-LDH@GO nanocomposites are lower than that of neat PP. The addition of nanoparticles provides a non-homogeneous nucleus for PP crystals, producing a heterogeneous nucleation mechanism that increases the spherulite density and decreases the spherulite size. The DOPOi-LDH@GO hinders the crystallization of PP and crushes spherulite integrity. The combination of LDH with GO for agglomeration-tolerant and LDH-modified at the interlamination and surface provides a potential way to improve the efficient dispersion and enhanced interfacial adhesion in the PP matrix. Thus, PP/DOPOi-LDH@GO nanocomposites exhibit a wide range of application potentials.