Persistent organic pollutants (POPs) have attracted significant attention because of their bioaccumulation, persistence, and toxicity. As anthropogenic products, POPs mainly contain polychlorinated biphenyls (PCBs), organochlorine pesticides (OPs), and polycyclic aromatic hydrocarbons (PAHs), and they pose a great threat to human health and the environment. To deal with these toxic contaminants, many different kinds of strategies for sensitively detecting POPs have been developed, such as high performance liquid chromatography (HPLC), surface enhanced Raman spectroscopy (SERS), and fluorescence. This paper mainly summarized the achievements of spectroscopy technologies, which generally consist of SERS, surface plasmon resonance (SPR), and fluorescence, in the detection of low-concentration POPs in different matrices. In addition, a retrospective summary is made on several critical considerations, such as sensitivity, specificity and reproducibility of these spectroscopy technologies in practical applications. Finally, some current challenges and future outlooks for these spectroscopy technologies are provided in regards to environmental analysis.