Design of three-dimensional metal oxide nanofibers by electrospinning is being widely explored. However, the impacts of calcination and sintering on the resulting morphology remain unknown. For the first time, (La0.6Sr0.4)(0.99)CoO3-delta (LSC) nanofiber, which is among the most promising electrode materials for solid oxide fuel cells, was synthesized by sol-gel electrospinning. By elevating the temperature in oxygen using in situ transmission electron microscopy, we discovered the structural transitions from nanofibers to nanotubes and then to nano-pearl strings. This facile and up-scalable method can be widely applied to design metal oxide one-dimensional nanomaterials with precise control in both geometry (nanofiber, nanotube and nano-pearl string) and surface area (by varying grain size).