A hydrophobic Cu grid was used as an electrospinning spinneret to fabricate ultrafine organic nanofibres. The Cu grid used in this study was that which holds samples in TEM. Due to the hydrophobic surface and larger contact angle of the electrospinning solution on the Cu grid surface, the solution flow was divided into several finer ones by the holes in the Cu grid instead of accumulating. Each finer flow was stretched into individual jets and established a multi-jet mode by the electrical field force. The finer jets played an important role in decreasing the diameter of the nanofibre. The charge repulsion force among charged jets enhanced the whipping instability motion of the liquid jets, which improved the uniformity of the nanofibre and decreased the diameter of the nanofibre. An ultrafine uniform nanofibre of diameter less than 80 nm could be fabricated directly with the novel Cu grid spinneret without any additive. This study provided a unique way to promote the application of one-dimensional organic nanostructures in micro/nanosystems.