Direct electrochemistry and electrocatalysis of myoglobin (Mb) were studied with Mb immobilized on dodecyltrimethylammonium bromide (DTAB) film modified carbon ceramic (CC) electrode. Cyclic voltammetry showed a pair of well-defined and nearly reversible redox peaks of Mb (FeⅡ/FeⅢ) at about -0.3 V vs. SCE (pH = 6.98). The currents of the redox peak were linear to scan rate, and rate constant (Ks) was estimated to be 3.03 s-1. The formal potential (E01) of Mb in the DTAB/CC electrodes shifted linearly with pH with a slope of-36.44 mV/pH, implying that the electron transfer between DTAB and CC electrodes is accompanied by proton transportation. The immobilized Mb exhibited excellent electrocatalytic response to the reduction of hydrogen peroxide (H2O2).