The nitrogen doped porous carbon nanopolyhedrons (N-PCNPs)-multi-walled carbon nanotubes (MWCNTs) hybrid materials were prepared for the first time. Combining the excellent catalytic activities, good electrical conductivities and high surface areas of N-PCNPs and MWCNTs, the simultaneous determination of hydroquinone (HQ), catechol (CC) and resorcinol (RE) with good analytical performance was achieved at the N-PCNPs-MWCNTs modified electrode. The linear response ranges for HQ, CC and RE are 0.2-455 ${mu}M$, 0.7-440 ${mu}M$ and 3.0-365 ${mu}M$, respectively, and the detection limits (S/N = 3) are $0.03{mu}M$, $0.11{mu}M$ and $0.38{mu}M$, respectively. These results are much better than that obtained on some graphene or CNTs-based materials modified electrodes. Furthermore, the developed sensor was successfully applied to simultaneously detect HQ, CC and RE in the local river water samples.