Diagnosing water infiltration is imperative to assess the integrity and operation performance of sewer networks, which is challenging and costly due to the complex nature of these networks. This study proposes a simple approach to evaluate the extent of groundwater infiltration via a fluorescence spectroscopy method, i.e., the identification and quantification of the fluorescent signature components of the dissolved organic matter sewage. A newly built sewer network in Shantou, Southern China, was selected for the case study, and a mass balance method based on water quality characteristic factors (total phosphorus and NH4+-N) was applied in parallel for comparison. The results showed that the mass balance method was substantially influenced by fluctuations in sewage and external water concentrations, rendering it unreliable due to the extensive data and calculations required. Conversely, three-dimensional excitation–emission matrix–parallel factor analysis enabled the identification of terrestrial humus compounds as the signatures of underground water sources. The estimation indicates that the groundwater proportion across the four surveyed inspection wells along the pipeline network ranged from 10.8 ± 2.5% to 9.6 ± 3.5%, conforming to the allowable groundwater infiltration limits set for municipal sewage pipelines (10–15%). This study presents a simple method for the in-depth analysis of groundwater infiltration in urban sewage networks, providing valuable insights into maintaining water quality and network integrity.