This article discusses the role of nanoscale calcium carbonate (nCC) surface treatment in affecting the mechanical, rheological, and thermal properties of linear low-density polyethylene (LLDPE). The mechanical tests indicated that nCC could simultaneously reinforce and toughen LLDPE. In addition, the composite sample with methacrylic acid (MA)-treated nanoparticles shows further increased mechanical properties as compared to unmodified nanoparticles. In the presence of dicumyl peroxide (DCP), a small amount of MA could increase markedly the mechanical properties of LLDPE/nCC composites. The results of rheological property analysis indicated that the viscosity increased with increasing amount of the filler, especially at low shear rates, but showed a substantial reduction with increasing concentration of the reactive monomer. The thermal behavior of these materials is evaluated by differential scanning calorimetry and thermogravimetric analysis. The addition of a small amount of MA and DCP enhances the stabilization of the blends.