Vanadium Pentoxide (V 2 O 5 ) is an appealing cathode candidate for Zinc-ion batteries (ZIBs) owing to its modifiable interlayer structure and changeable chemical redox states. However, the extensive practical application is deeply plagued by either poor rate capability or cycling stability performance. Herein, the methyl group decorated V 2 O 5 with hydrangea-like morphology was successfully fabricated by a facile solvothermal method to solve the problem. Such a hydrangea-shaped architecture containing numerous nanosheets is advantageous for the rapid ions/electrons transfer. The extended interlayer distance stemmed from the pillar effect of the methyl-functionalized V 2 O 5 contributes a comparatively steady and rapid Zn 2+ intercalation/deintercalation. When applied in ZIBs, it delivers a superior rate capability (123 mA h g −1 at 4.0 A g −1 ) and an excellent long-life cycling (capacity retention of 112.7 % after 1000 cycles at 4.0 A g −1 ). Electrochemical kinetics investigations of methyl-functionalized V 2 O 5 microsphere show that the capacity is dominantly contributed from pseudocapacitance. As well, mechanism of zinc ion storage has been explored. Such a structural design of electrode materials can be exploited to promote extensive applications of ZIBs in future. Pillaring effect of methyl group in the hydrangea-like V 2 O 5 microsphere ensures the expanded interlayer spacing for advanced Zn storage. • Methyl-functionalized V 2 O 5 is successfully prepared via a simple solvothermal method. • Pillaring effect of methyl group endows the favorable interlayer expansion and structural stability. • Methyl-functionalized V 2 O 5 is a promising cathode material for Zn-ion batteries.