Morphological evolution accompanying a surface roughening and preferred orientation is an effective way to realize a high-performance gas sensor because of its significant potential as a chemical catalyst through chemical potentials and atomic energy states. In this work, we investigated a heterojunction of double-side-W-decorated NiO nanoigloos fabricated through radio frequency sputtering and a soft-template method. Interestingly, a morphological evolution characterized by a pyramidal rough surface and the preferred orientation of the (111) plane was observed upon decorating the bare NiO nanoigloos with W. The underlying mechanism of the morphological evolution was precisely demonstrated based on the van der Drift competitive growth model originating from the oxygen transport and chemical strain in the lattice. The gas sensing properties of W-decorated NiO show an excellent NO2 response and selectivity when compared to other gases. In addition, high response stability was evaluated under interference gas and humidity conditions. The synergistic effects on the sensing performance were interpreted on the basis of the morphological evolution of W-decorated NiO nanoigloos.