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In the recent times, pseudocapacitive electrode materials have received great attention due to their considerable capability in storing ions at relatively fast charging rates. Among various candidates, niobium (V) pentoxide (Nb 2 O 5 ) has gained much attraction for lithium-ion batteries (LIBs) due to its insertion/extraction reaction with Li, safe redox potential, and considerably good capacity (about 200 mAhg −1 ). Nevertheless, low conductivity of Nb 2 O 5 has so far prevented its use as a viable electrode material for LIBs. In this study, we have successfully coated silver (Ag) nanoparticles (NPs) on the surface of one-dimensional orthorhombic Nb 2 O 5 fiber (1D T-Nb 2 O 5 ) using simple electrospinning processing. Ag NPs coated Nb 2 O 5 fibers (Ag-1D T-Nb 2 O 5 ) provided faster electron pathways, resulting in much improved capacity at a given current density with superior rate capabilities compared with pristine 1D T-Nb 2 O 5 . In addition, 1D T-Nb 2 O 5 was more suitable for coating Ag NPs compared with T-Nb 2 O 5 NPs, where its structural integrity was maintained even after cycling. As a result, effective coating of conductive Ag NPs on the 1D T-Nb 2 O 5 resulted in excellent cycle retention characteristics (179.7 mAhg −1 after 500 cycles at 500 mA g −1 ) as well as superior rate capabilities (103.6 mAhg −1 at a current density of 5000 mA g −1 ). [ABSTRACT FROM AUTHOR]