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PVDF nanofibre-based piezoelectric nanogenerators are directly prepared via electrospinning without any post-poling treatment. The effect of the addition of multi-walled carbon nanotubes (MWCNTs) on the fibre diameter, mechanical properties, β-phase composition, surface and volume conductivities, output voltage and output power are investigated. Increased surface conductivity of the poly-vinylidene fluoride (PVDF) nanofibre mats, which plays an important role in the enhancement of output power, is first found by the addition of an appropriate amount of MWCNTs. The maximum generated piezo-voltage exhibited by PVDF nanofibre mats in the presence of 5 wt% MWCNTs is as high as 6 V, while the average capacitor charging power is 81.8 nW, increases of 200% and 44.8%, respectively, compared with bare PVDF nanofibre mats.