2D layered molybdenum disulfide (MoS2) has garnered considerable attention as an attractive electrode material in sodium-ion batteries (SIBs), but sluggish mass transfer kinetic and capacity fading make it suffer from inferior cycle capability. Herein, hierarchical MoS2 nanosheets decorated porous TiO2 nanofibers (MoS2 NSs@TiO2 NFs) with rich oxygen vacancies are engineered by microemulsion electrospinning method and subsequent hydrothermal/heat treatment. The MoS2 NSs@TiO2 NFs improves ion/electron transport kinetic and long-term cycling performance through distinctive porous structure and heterogeneous component. Consequently, the electrode exhibits excellent long-term Na storage capacity (298.4mAhg-1 at 5Ag-1 over 1100 cycles and 235.6mAhg-1 at 10Ag-1 over 7200 cycles). Employing Na3V2(PO4)3 as cathode, the full cell maintains a desirable capacity of 269.6mAhg-1 over 700 cycles at 1.0Ag-1. The stepwise intercalation-conversion and insertion/extraction endows outstanding Na+ storage performance, which yields valuable insight into the advancement of fast-charging and long-cycle life SIBs anode materials.