Chemical vapor generation (CVG) is widely used in analytical atomic spectrometry, with advantages of high efficiency of sample introduction (vapor generation and transportation) and matrix separation. Photochemical vapor generation (Photo-CVG) is a new subset of CVG and it has been demonstrated a powerful alternative to conventional CVG techniques due to its inherent advantages. For a long time, most research works have been devoted to improving vapor generation efficiency and expanding the vaporable element scope of Photo-CVG. Nowadays, with the help of nanomaterials and enhancement reagents, Photo-CVG covers a wide range of detectable elements and the vapor generation efficiency of some elements has been improved significantly. In this review, we summarizes the developments and applications of nanomaterials/enhancement reagents assisted Photo-CVG for analytical atomic spectrometry, including TiO₂ and TiO₂-based composites, MOFs and some metal ions utilized as photocatalysts, photo-oxidation/reduction and enhancement reagents; as well as nanomaterials for preconcentration/separation in Photo-CVG systems.