Noninvasive and real‐time detection of bilirubin concentration enables rapid assessment of liver health status and the diagnosis of jaundice‐related diseases. Herein, the study proposes a strategy to uniformly grow bimetallic FeCo metal–organic framework (MOF) films onto the surface of carbonized electrospun nanofibers via a stepwise growth strategy involving an induction effect of oxide nanomembrane prepared by atomic layer deposition, to realize high‐performance flexible nanofiber bilirubin sensors. Compared with monometallic MOF, the FeCo bimetallic MOF can attain a larger specific surface area, thus augmenting the exposed active sites. Furthermore, the synergistic interaction between the bimetallic active sites on the MOF film and the carbonized nanofibers enhances the electronic conduction network, thereby significantly enhancing the catalytic activity of the flexible electrode for bilirubin. The current nanofibers sensor exhibits excellent performance in bilirubin detection, in terms of high sensitivity, large linear detection range, and low detection limit. The synthesis of bimetallic MOF films on flexible fibers holds promise for the development of highly sensitive electrodes for wearable bilirubin detection devices.