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Polydimethylsiloxane (PDMS) is the most widely used silicon-based organic polymer, and is particularly known for its unusual rheological properties. PDMS has found extensive usage in various fields ranging from microfluidics and flexible electronics to cosmetics and food industry. In certain applications, like e.g. dry adhesives or dry transfer of 2D materials, adhesive properties of PDMS play crucial role. In this review we focus on probing the mechanical and adhesive properties of PDMS by means of atomic force microscopy (AFM). Main advantages and limitations of AFM-based measurements in comparison to macroscopic tests are discussed.