Electrified methanol steam reforming (MSR) assisted by nonthermal plasma (NTP) is a pivotal enabler for clean hydrogen production at ambient conditions with several advantages. This study optimizes the NTP‐assisted MSR by catalyst engineering, as well as membrane technology (via a 2D MXene nanosheet membrane reactor). Our findings reveal that active‐phase engineering in catalyst design is crucial in regulating MSR pathways under NTP conditions with the bimetallic Ni–Cu alloys enhancing the H2 production via surface water–gas shift reaction (WGSR). Additionally, integrating a MXene membrane within a dielectric barrier discharge (DBD) NTP reactor enabled the reactive‐separation process, improving methanol conversion, H2 formation rate with higher purity, as well as showing a good stability.