AbstractIon‐based electrochemical random‐access memory (ECRAM) is proposed for synaptic applications owing to its promising characteristics that have the potential to accelerate data processing through neuromorphic systems. However, attaining ideal synaptic functionalities and constructing high‐density vertical synapse arrays are challenging due to issues related to uncontrolled ion migration and constraints in 3D multi‐stacking. Here, a breakthrough using 3D stackable Li ion‐based vertical‐sensing ECRAM (VS‐ECRAM) is presented with an ion‐permeable ultrathin WS2 electrode synthesized through low‐temperature (200 °C) atmospheric‐pressure plasma‐enhanced chemical vapor deposition (AP‐PECVD). The direct AP‐PECVD of the WOx channel layer induces WS2 formation in the surface region, which exhibits sufficient electrical conductivity to function as an electrode. By utilizing the WS2 electrode as an ion‐barrier layer in the VS‐ECRAM synapse, excellent weight update linearity and cycling variability are achieved due to the finely controlled ion migration. Furthermore, a two‐layer stacked 3D VS‐ECRAM is successfully fabricated through the vertical WS2 formation, and independent weight updates without any disturbance are confirmed. Finally, a high pattern recognition accuracy of 95.22% is obtained using a multi‐layer perceptron‐based neural network. Therefore, the proposed 3D stackable WS2‐based VS‐ECRAM exhibits a strong potential for application in high‐density neuromorphic devices with excellent synaptic performances.