This paper studies a W-band high-order harmonic peniotron with magnetron resonant system, which has the merits of high efficiency, low external magnetic field and low operation voltage. By solving the dispersion relation of the resonant system, the relation between the resonant system and the selection of harmonics has been pointed out. The primary design of an 11-vane high-order harmonic peniotron working in 2π mode has been completed. Three-dimensional PIC simulation and optimization results show that this device can produce an average output power of 8.6 kW with 28.7% efficiency at 99.1 GHz, under the external magnetic field of 0.379 T, velocity ratio of 2, and operation voltage and current of 30 kV and 1 A, respectively.