The invention discloses an online measurement device and measurement method for the NO concentration in a high-NO2 and low-NO atmosphere. The online measurement device comprises an ozone generation unit, a connection pipe cleaning unit and a sampling pipe, wherein a connection reaction bin, an NO2 measuring instrument, a second mass flow meter and a first air pump are sequentially connected behind the sampling pipe; and the connection pipe cleaning unit comprises an electromagnetic three-way valve, an activated carbon tube, a current-limiting hole and a second air pump. By adopting a cavity-enhanced absorption spectroscopy, a sampling mode (actual atmosphere of ozone is added) or a zero point mode (actual atmosphere) is set through the electromagnetic three-way valve; absorption spectrum intensity signals of two modes are measured through an NO2 measuring instrument as a sampling spectrum and a reference spectrum respectively, and then NO in the atmosphere is converted into a concentration value of the NO2 through spectral fitting, that is to say, measurement of the NO concentration in the atmosphere environment is achieved, so that the online measurement device and measurement method have the characteristics of being free of NO2 concentration interference, a low detection limit, high sensitivity, high temporal-spatial resolution, high stability and low cost.