The rapid growth in commercial use of silver nanoparticles (AgNPs) will inevitably increase silver exposure in the environment and the general population. As the fate and toxic effects of AgNPs is related to the Ag(+) released from AgNPs and the transformation of Ag(+) into AgNPs, it is of great importance to develop methods for speciation analysis of AgNPs and Ag(+). This study reports the use of Triton X-114-based cloud point extraction as an efficient separation approach for the speciation analysis of AgNPs and Ag(+) in antibacterial products and environmental waters. AgNPs were quantified by determining the Ag content in the Triton X-114-rich phase with inductively coupled plasma mass spectrometry (ICPMS) after microwave digestion. The concentration of total Ag(+), which consists of the AgNP adsorbed, the matrix associated, and the freely dissolved, was obtained by subtracting the AgNP content from the total silver content that was determined by ICPMS after digestion. The limits of quantification (S/N = 10) for antibacterial products were 0.4 μg/kg and 0.2 μg/kg for AgNPs and total silver, respectively. The reliable quantification limit was 3 μg/kg for total Ag(+). The presence of Ag(+) at concentrations up to 2-fold that of AgNPs caused no effects on the determination of AgNPs. In the cloud point extraction of AgNPs in antibacterial products, the spiked recoveries of AgNPs were in the range of 71.7-103% while the extraction efficiencies of Ag(+) were in the range of 1.2-10%. The possible coextracted other silver containing nanoparticles in the cloud point extraction of AgNPs were distinguished by transmission electron microscopy (TEM), scanning electron microscopy (SEM)- energy dispersive spectroscopy (EDS), and UV-vis spectrum. Real sample analysis indicated that even though the manufacturers claimed nanosilver products, AgNPs were detected only in three of the six tested antibacterial products.