Microchannel plate (MCP), a high‐porosity glass membrane used as an electron multiplier in analytical/scientific instruments for the detection of energetic photons and charged particles is demonstrated here as a highly effective bipolar electrode (BPE) for electrokinetic focusing of anions. Assembled between a pair of microfluidic channels filled with an electrolyte buffer and subjected to a sufficient bias potential, MCP supports faradaic reactions, owing to its semiconducting characteristics. Thousands of microcapillary tubes fused together define MCP and act in unison such that each microcapillary serves as a tiny BPE surrounding an infinitesimal element of bulk electrolyte with a large surface‐area‐to‐volume ratio and hence performs highly effective as compared to a planar electrode inlaid into a microchannel. This performance has been validated here where concentration enrichment of a fluorescent tracer has been demonstrated at a remarkable rate of up to 175‐fold/s exceeding those reported for planar BPEs. We attribute such high performance to the rapid onset of ion‐depletion zone and subsequent steep field gradient, signifying the high‐porosity structure of MCP as an effective BPE.