Electrospinning and galvanic displacement reaction are combined to fabricate ultra-long hollow chalcogen and chalcogenide nanofibers in a cost-effective and high throughput manner. This procedure exploits electrospinning to fabricate ultra-long sacrificial nanofibers with controlled dimensions and morphology, thereby imparting control over the composition and shape of the nanostructures evolved during galvanic displacement reaction. It is believed to be a general route to form various ultra-long hollow semiconducting nanofibers.