By its decision SC-4/31 on global monitoring plan (GMP) for effectiveness evaluation, the Conference of the Parties of the Stockholm Convention at its fourth meeting in 2009 requested, among others, updating the guidance document for the GMP with additional chapters on long-range transport, specimen banking and the impact of listing new chemicals into annexes of the Convention. At the same meeting, decision SC-4/17 listed perfluorooctane sulfonic acid (PFOS), its salts and perfluorooctane sulfonyl fluoride in the annex B of the Convention. The addition of new chemicals to the list of persistent organic pollutants (POPs) implies the updating and development of relevant guidance, such as for POPs monitoring under the effectiveness evaluation. In order to assist in this task, the Chemicals Branch of the United Nations Environment Programme (UNEP) executed the project ‘Establishing the Tools and Methods to Include the Nine New POPs into the Global Monitoring Plan (GMP)’, which was implemented from 2011 to 2015 and financed by the Global Environment Facility (GEF). The objective of the project was to update the guidance for POPs GMP by recommending analytical methods for the analysis of the newly listed POPs. Further, it was recommended to include surface water as an additional matrix for PFOS. The usefulness of the matrices is as follows: air or water receive the emissions of the POPs from the source and transport them around the globe; human milk or blood characterizes human exposures at a significant stage in development.