Since ultraviolet radiation is one of the major environmental factors that cause photoageing/photodamage, human hair, including both dyed and undyed hair, are subject to color change following extended exposure to sunlight. In the work described in this paper, six samples of human hair from Chinese volunteers that included untreated, bleached and dyed were subjected to accelerated ageing by exposure to UVA (320～400 nm) radiation. Changes to their chemical compositions during photoageing were non-destructively characterized by reflectance, 3D-fluorescence and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopies. These techniques, together with a quantitative analysis of the photosensitized generation of hydrogen peroxide, were used to assess the effects of different hair color and bleaching/dyeing treatments on the light stability of hair fibers. The results suggest that UVA irradiation can induce the production of hydrogen peroxide via a type Ⅱ mechanism (electron transfer interaction between photosensitive protein groups in their excited states) and subsequent reaction with oxygen, resulting in photo-oxidative degradation of surface protein and pigments of the hair fiber. Hair fibers of natural or artificial color respond differently in terms of color change during photoageing. Natural white and gray hair fibers exhibited the usual photoyellowing; and chemically black-dyed and bleached hairs showed photofading and additional photobleaching, respectively. Irradiation of hair in the wet state was found to accelerate photodegradation. Chemical bleaching and oxidative dyeing processes were shown to promote the photoinduced production of hydrogen peroxide, which contribute to a higher level of oxidative stress and thereby affects the photostability of human hair. Pigment molecules in hair, including both the natural pigmentation of melanin and that produced by artificial dyes, are suggested to play a dual role, both in the production and in the scavenging of oxygen free radicals. The work is designed to contribute to the establishment of spectroscopic methods for assessing the extent of hair photodamage as well as providing a sound experimental data basis for the research and development of improved hair dyes and after-dye products for the Chinese cosmetic market.