An effective route has been developed (see Figure) to fabricate 3D ZnS nanoarchitectures. Twin crystals of ZnS whiskers are first fabricated, onto which nanobranches are grown that are sheathed with BN shells. Arrays of ZnS nanobranches were crystallographically aligned on ZnS twin crystals forming ordered nanoarchitectures. The insulating and protecting sheath of BN was completely coated on the ZnS nanoarchitectures to enhance their stability.