Nanofluidic devices have turned out to be exemplary systems for investigating fluidic transport properties in a highly restricted area, where the electrostatic interactions or chemical reactions between nanochannel and flowing species strongly dominate the ions and flow transport. Numerous nanofluidic devices have recently been explored to manipulate ion currents and construct electronic devices. Enlightened by electronic field effect transistors, utilizing the electric field effect of nanopore nanochannels has also been adopted to develop versatile nanofluidic devices. Here, we report a nanopore-based nanofluidic unijunction transistor composed of a conical glass nanopipette with the biomaterial polydopamine (PDA) coated at its outer surface. The as-fabricated nanofluidic device exhibited negative differential resistance (NDR) and ion current oscillation (ICO) in ionic transport. The pre-doped copper ions in the PDA moved toward the tip as increasing the potential, having a robust shielding effect on the charge of the tip, thus affecting the surface charge density of the nanopore in the working zone. Finite element simulation based on a continuum model coupled with Stokes–Brinkman and Poisson–Nernst–Planck (PNP) equations revealed that the fluctuations in charge density remarkably affect the transport of ionic current in the nanofluidic device. The as-prepared nanofluidic semiconductor device was a ready-to-use equipment that required no additional external conditions. Our work provides a versatile and convenient way to construct nanofluidic electronic components; we believe by taking advantage of advanced surface modification methods, the oscillation frequency of the unijunction transistors could be controlled on demand, and more nanofluidic devices with resourceful functions would be exploited.