Flexible dopamine (DA) sensors were fabricated with ordered mesoporous carbon-covered carbonized silk fabrics (OMC/CSFs) as the working electrodes. These free-standing OMC/CSF electrodes were derived from the co-assembly of resol and block polymers with CSFs as substrates and subsequent carbonization of the resulting composites. As a result, a homogeneous OMC layer with vertically aligned ordered mesopore arrays grew on the surface of the CSFs, which effectively influenced the electrochemical detection behavior of OMC/CSFs towards DA. Using the flexible OMC/CSF electrodes, the electrochemical DA sensors exhibited high sensitivity, good selectivity, a large linear detection range of 0.2-80 μM, and a low limit detection of 0.11 μM, which were better than those of recently reported flexible DA sensors based on precious-metal-free electrodes.