Enhancing catalytic activity is the key to develop electrochemical sensors for monitoring of neonicotinoid such as imidacloprid (IMI), thiamethoxam (THX) and dinotefuran (DNF). Herein, a MOF-derived octahedral NiCu nanoporous carbon composite with abundant N-doped (N/NiCu@C) was synthesized, which was exploited as electrochemical sensor for neonicotinoid determination. Integrating the synergistic effect of NiCu nanoalloy and the hierarchical porous carbon structure, the N/NiCu@C/GCE significantly promoted the diffusion between electrolyte and active site. Meanwhile, the introduction of polyvinylpyrrolidone (PVP) improved the hydrophilicity and dispersibility of N/NiCu@C, endowing superior electrocatalytic performance for IMI, THX and DNF determination, with linear ranges of 0.5-60, 1-60 and 0.5-60 μM, respectively, and detection limits of 0.017, 0.007 and 0.001 μM. Additionally, the sensor can determine IMI, THX and DNF in apples, tomatoes and potatoes with the recovery rate of 92.1-103.4% and RSD ≤ 4.7%. This study has explored a novel modified electrode material for construction of neonicotinoid sensors.