This paper is devoted to the investigation of the photooxidation of poly(N-vinylcarbazole (PVK) and polyethylene (LDPE) by exposure to λ ≥ 300 nm polychromatic light (SEPAP 12.24) or UV light produced by a new setup equipped with LEDs emitting at 365 nm (LED 365), both at a temperature of 60 °C. Photooxidation was studied by infrared and UV-visible spectroscopies and emission spectroscopy in the case of PVK. The mechanisms by which the oxidation products were formed in both polymers were recalled. Depending on the conditions of ageing, i.e., polychromatic light or exposure to LED 365, the same oxidation products were obtained but with different rates and different relative amounts. This result reflected the influence of the wavelengths on the mechanisms. In the case of PVK, the formation of oxidation photoproducts and yellowing were not impacted, but the kinetics of the decrease in excimer fluorescence, which is linked to the crosslinking of the polymer, were dramatically modified. In the case of LDPE, wavelength effects on the photolysis of ketones by Norrish reactions were observed. As a consequence, irradiations with the LED 365 setup could not be claimed to be representative of polychromatic irradiations because the shortest wavelengths ((300 nm < < 350 nm)) were missing and could not reproduce natural outdoor conditions of weathering.