NaFeAs recently observed superconductivity with the maximum $T_c{approx}25$ K is investigated using first principles approach. We will address briefly the electronic structure and contrast other superconducting pnictides. This system shows strong two-dimensionality and reduction of flatness in the Fermi surfaces undermines tendencies of magnetic or charge instabilities. As observed in other superconducting pnictides, $Q_M=(pi,pi,0)$ antiferromagnetic ordering, which has not been observed clearly yet in this compound, is energetically favored. However, contrast to other superconducting pnictides, the density of states in this ordering shows considerable electron-hole asymmetry, implying efficiency of hole-doping than electron-doping to enhance $T_c$.