With multiple signal channels, array sensing can effectively improve detection selectivity, but at the cost of increasingly complex analytical operation and decreased repeatability. Herein, we propose a “single MOF-based sensor array” in which a white-light-emitting MOF is used to provide multiple response channels with its manifold emission bands to overcome these drawbacks; the potential of this strategy was verified by the discrimination of berberine homologues (a sub-class of isoquinoline-type alkaloids). A white-light-emitting MOF was synthesized by the incorporation of three luminescent ligands into the UiO-66 backbone. With distinct response behaviors, these components could produce a three-channel signal pattern for the analyte. Thus, this MOF realized array sensing with a single measurement of its spectrum. Its discrimination limit for berberine homologues was as low as 2 μM, and by combination with chemical titration, this MOF could identify samples with unknown concentrations. This work demonstrates the advantage of white-light-emitting MOFs in array sensing.