Memristors, i.e., short for resistor with memory, are electronic devices that can switch their electrical resistance between different levels depending on the external voltages applied. [1] The resistive switching (RS) phenomenon was first observed in the late 1960s in a two-terminal cell based on a phase-change material sandwiched by two electrodes, [2] and nowadays it has been observed in many other materials (e.g., metal-oxide, magnetic, and ferroelectric thin films). [3] The performance of memristors is characterized by the voltage, energy, and time that they need to switch, as well as by the resistance of each state, the stability of the state resistance over time (i.e., retention time), and the maximum number of cycles that it can switch (i.e., endurance). [4,5] Depending on the materials employed to fabricate the memristor its main figures-of-merit may vary, allowing its use in multiple applications, such as non-volatile memory, advanced computation, radiofrequency switches, and entropy source for encryption systems. [3,6] The use of memristors in the field of bioelectronics is highly desired because they could enormously simplify the structure of integrated circuits required for spiking signal detection [7] and event-driven operation [8] -i.e., two key functions in multiple products, such as e-skin and monitoring systems-plus they may enable more sophisticated functionalities, such as in-memory computing, [9] and neuromorphic computation by reverse engineering the brain. [10] As an example, reference [11] employed bio-compatible organic memristors to monitor the signal activity of neocortical pyramidal neurons from rats, and reference [12] reported a three-neuron brain-silicon network to emulate transmission and plasticity properties of real synapses. However, in such studies, a patch-clamp integrated circuit was required to amplify the bioelectronic signal from the living cells (i.e., 50-100 mV) to the operational voltages of the memristors (i.e., >2 V), which increased the complexity of the overall system. Therefore, fabricating memristors capable to operate at low bio-compatible voltages is highly attractive to simplify the circuitry and reduce the energy consumption of bioelectronic systems, which may enable their use in battery-less and selfpowered implants.Many studies have attempted the fabrication of memristors with ultralow switching voltages (see Table S1, SupportingThe development of memristors operating at low switching voltages <50 mV can be very useful to avoid signal amplification in many types of circuits, such as those used in bioelectronic applications to interact with neurons and nerves. Here, it is reported that 400 nm-thick films made of dalkyl-dithiophosphoric (DDP) modified copper nanoparticles (CuNPs) exhibit volatile threshold-type resistive switching (RS) at ultralow switching voltage of ≈4 mV. The RS is observed in small nanocells with a lateral size of <50 nm -2 , during hundreds of cycles, and with an ultralow variability. Atomistic calculations reveal that the switching mech...