Recent progress in nanoscience and nanotechnology creates new opportunities in the design of novel SnO2 nanomaterials for photocatalysis and photoelectrochemical. Herein, we firstly highlight a facile method to prepare three- dimensional porous networks of ultra-long SnO2 nanotubes through the single capillary electrospinning technique. Compared with the traditional SnO2 nanofibers, the as-obtained three-dimensional porous networks show enhancement of photocurrent and photocatalytic activity, which could be ascribed to its improved light-harvesting efficiency and high separation efficiency of photogenerated electron–hole pairs. Besides, the synthesis route delivered three-dimensional sheets on the basis of interwoven nanofibrous networks, which can be readily recycled for the desirable circular application of a potent photocatalyst system.