Polyamide 66 (PA66)/montmorillonite composite nanofibres were prepared by electrospinning using formic acid and dichloromethane as solvent. The morphology and diameter of the produced nanofibres were studied by SEM. The results reveal that the average diameter of produced electrospun PA66 and PA66/montmorillonite nanofibres is (67±18) nm and (63±13) nm, respectively. FT-IR illustrate the hydrogen bonding formed between PA66 and montmorillonite. The nanocomposites fibres exhibit higher thermal stability through TG analysis; the initial decomposition temperature and the maximum decomposition temperature increases 26°C and 39°C, respectively. Ultraviolet aging test shows that PA66/montmorillonite composite nanofibres have higher ultraviolet aging resistance for the lamella shielding effect of montmorillonite; meanwhile, hygroscopicity test shows that the composite nanofibres have higher hydrolysis resistance for 67.3% decline in the water absorption. Electrospun nanocomposites can be alternative candidates for developing novel PA66/clay nanofibers with high performance.