In this report, a graphene/poly(ethylene-co-vinyl acetate) composite electrode was fabricated by melt compounding for the amperometric detection of capillary electrophoresis. The composite electrode was fabricated by packing a mixture of graphene and melted poly(ethylene-co-vinyl acetate) in a piece of fused silica capillary under heat. The structure of the composite was investigated by scanning electron microscopy and Fourier transform infrared spectroscopy. The results indicated that graphene sheets were well dispersed in the composite to form an interconnected conducting network. The performance of this unique graphene-based detector has been demonstrated by separating and detecting rutin, quercitrin, kaempferol, and quercetin in Cacumen platycladi in combination with capillary electrophoresis. The four flavones have been well separated within 9 min in a 50-cm-long capillary at a separation voltage of 12 kV using a 50 mM sodium borate buffer (pH 9.2). The graphene-based detector offered significantly lower operating potentials, substantially enhanced signal-to-noise characteristics, lower expense of operation, high resistance to surface fouling, and enhanced stability. It showed long-term stability and repeatability with relative standard deviations of <5% for the peak current (n = 15).