A novel composite material, hybrid zeolitic imidazolate framework (HZIF)–conducting poly(3,4-ethylenedioxythiophene) (PEDOT) has been fabricated on carbon cloth electrode (CCE) by microwave-assisted crystallization, followed by drop-coating and vapor deposition procedures. Specifically, the HZIF inserted by molybdenum (HZIF-Mo) is entitled to intrinsic catalytic activity towards amine molecules, which is firstly integrated with the conductive and catalytic PEDOT as an enhanced electrochemical sensor for hydroxylamine. Detection is performed by amperometric method, and the composite sensor (HZIF-Mo/PEDOT/CCE) shows a low detection limit of 0.04 μM (S/N = 3) in the linear range of 0.1–692.2 μM, along with superior anti-interference ability, reproducibility (RSD = 4.43%) and outstanding performance in real samples. As noticed, the hydroxylamine catalytic process combines the advantages of the alkaline-stable HZIF-Mo containing ample catalytic sites and high surface area and the mesoporous PEDOT reining in outstanding conductivity and redox capability, thereby imparting amplified electrochemical signals. This work undertakes an opening to expand MOF-based composites for versatile sensing applications.