Here we report the first observation of active waveguide of electrochemiluminescence (ECL) in single crystalline molecular wires self‐assembled from cyclometalated iridium(III) complexes, namely tris(1‐phenylisoquinoline‐C2, N) (Ir(piq)3). Under dark conditions, the molecular wires deposited on the electrode surface can act as both ECL emitters and active waveguides. As revealed by ECL microscopy, they exhibit the typical characteristics of optical waveguides, transmitting ECL and generating much brighter ECL emission at their terminals. Moreover, self‐generated ECL can be confined inside the molecular wire and propagates along the longitudinal direction as far as ≈100 μm to the terminal out of touch with the electrode. Therefore, this one‐dimensional crystalline molecular wire‐based waveguide offers the opportunity to switch the electrochemically generated ECL to remote light emission in non‐conductive regions and is promising for contactless electrochemical analysis and study of (bio)chemical systems.