The collision involved one car – a silver Mercedes E220 estate – and officers attended to assist with traffic management.
Paramedics from the Welsh Ambulance Service also attended and confirmed that a 49-year-old man from Box in Wiltshire had died at the scene.
His next of kin have been informed and are receiving support from specialist officers.
Anyone with information about the collision is asked to get in touch with Gwent Police.
They are asking for anyone who may have witnessed the collision or any motorists with dashcam footage that were using the A40 between 1.45pm and 2.15pm and between Abergavenny and Raglan to contact them.
You can call Gwent Police on 101 or send them a direct message on Facebook or Twitter, quoting log reference 2200018109, with any details.
Alternatively, you can call Crimestoppers anonymously on 0800 555 111.
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