AgNPs have exceptional characteristics that depend on their size and shape. Over the past years, there has been an exponential increase in applications of nanoparticles (NPs), especially the silver ones (AgNPs), in several areas, such as, for example, electronics; environmental, pharmaceutical, and toxicological applications; theragnostics; and medical treatments, among others. This growing use has led to a greater exposure of humans to AgNPs and a higher risk to human health and the environment. This risk becomes more aggravated when the AgNPs are used without purification or separation from the synthesis medium, in which the hazardous synthesis precursors remain unseparated from the NPs and constitute a severe risk for unnecessary environmental contamination. This review examines the situation of the available separation methods of AgNPs from crude suspensions or real samples. Different separation techniques are reviewed, and relevant data are discussed, with a focus on the sustainability and efficiency of AgNPs separation methods.