A flexible composite paper Fe−Cu‐based metal‐organic framework (MOF)/reduced graphene oxide (rGO) (Fe−CuMOF/rGO) electrode was prepared by using a simple electrochemical method for the simultaneous detection of catechol (CC) and resorcinol (RC). Free‐standing, flexible and double‐sided Fe−CuMOF/rGO composite paper was obtained by applying the electrochemical deposition process on the rGO paper electrode in the solution containing Fe−CuMOF composite. The morphological analysis of Fe−CuMOF/rGO composite paper showed that sea urchin‐like structures formed on the rGO electrode surface consist of numerous sharp‐edged nanorods of Fe−CuMOF. Flexible Fe−CuMOF/rGO paper electrode exhibited high sensitivity, wide linear range and low detection limit for the simultaneous determination of CC and RC. The linear ranges of concentration for CC and RC were 0.1–800 and 0.1–720 μM, respectively, and the corresponding limits of detection (S/N=3) were 0.016 and 0.020 μM. The outstanding performance of this flexible electrode could be attributed to the sharp‐edged urchin‐like Fe−CuMOF structures which provide an increment of the surface area and the electrochemical activity of the composite paper electrode. Stability tests showed that Fe−CuMOF/rGO composite paper electrode has excellent flexibility, high durability, and good reproducibility. Furthermore, this electrode exhibited high sensitivity and selectivity for the determination of CC and RC in real sample analysis.