Archaea have multiple roles in global biogeochemical cycles. However, we still have limited knowledge about how environmental factors affect the diversity and function of different archaeal lineages. The goal of this study was to examine the change in the abundance and community structure of Archaea in the sediments collected from the lower Pearl River (mainly North River tributary), its estuary, and coastal South China Sea (SCS) in order to evaluate how archaeal ecological function might change along the salinity gradient. Pyrosequencing of the 16S rDNA gene of Archaea was performed on sediment samples from Feilaixia Dam on the North River tributary to Wanshan islands, which have a salinity range of 0.1 to 31.2 aEuro degrees. Consistent with the salt tolerance of cultivated representatives, methanogens in the genera Methanoregula, Methanosaeta, and Methanosarcina and Nitrososphaera within Thaumarchaeota of the ammonia-oxidizing Archaea (AOA) were abundant in freshwater sediments of the North River tributary, whereas the marine-associated genera Methanococcoides and Nitrosopumilus were the most abundant methanogens and AOA, respectively, in the estuary and coastal SCS. However, the percentages of total methanogens decreased and Thaumarchaeota increased with salinity, respectively. The phylum Crenarchaeota was largely represented by class-level lineages with no cultivated representatives, which collectively were more abundant in the estuary and coastal SCS in comparison to freshwater sites. This study indicates that salinity is the dominating factor affecting archaeal community structure and ecological function from the North River tributary of the Pearl River, its estuary, and coastal SCS, which is consistent with salinity control on microbial diversity in other regions of the world.