We have developed a new controllable method of selective and nonselective deposition of high quality aluminum by low‐pressure chemical vapor deposition using dimethylaluminum hydride with hydrogen. At first, silicon dioxide via holes on silicon substrate were selectively filled with aluminum by thermal decomposition. Then, adding the plasma excitation for 1 min, the aluminum film began to deposit nonselectively on the silicon dioxide as well as the selectively deposited aluminum. Silicon dioxide via holes were completely planarized by the selective and nonselective deposition. The single‐crystal structure of aluminum deposited selectively on silicon was observed with a new scanning microreflection high‐energy electron diffraction microscope.