In this work, we prepared new poly(vinyl alcohol) (PVA) based magnetic-pH responsive smart gels comprised of nickel nanoparticles and cross-linked PVA with a pH responsive poly(methyl methacrylic acid) (PMAA) (designated as (PVA-PMAA/Ni-NCGs). We developed a strategy based on the modification of PVA with glycidyl methacrylate (GMA) groups, which has the advantage of being highly efficient in preparing cross-linked PVA with pH responsive polymer chains. The PVA(GMA)-PMAA/Ni-NCGs were characterized by X-ray diffraction, scanning electron microscopy, magnetic measurements and thermogravimetric analysis. We report the relationship between macroscopic properties like the swelling ratio and the network microstructure of PVA(GMA)-PMAA/Ni-NCGs. Swelling in water and drying in air were alternately repeated, in which water was exchanged by new water before each swelling experiment. The PVA(GMA)-PMAA/Ni-NCGs can respond to a magnetic field and the pH changes of an environment. We present an example showing that PVA(GMA)-PMAA/Ni-NCGs can be innovatively exploited as a polymeric material in the application of controlled drug release.