Here, the formation of responsive polymeric materials with tunable response time is reported. These structures are fabricated by chemically modifying poly(vinylmethyl siloxane) (PVMS) networks with alkanethiols bearing a hydrophilic end-group (-COOH or -OH). The response time is facilitated by the liquid nature of the PVMS backbone and increases with increase in length of the methylene spacer (-CH2)(n)- in the alkanethiol pendent group. While for n = 2 and 6, the surface reconstructs almost instantaneously, specimens with n = 11 resist reconstruction because of strong van der Waals forces, leading to the formation of semi-crystalline regions. It is demonstrated that the responsive nature of PVMS-S-(CH2)(11)OH can be fine-tuned by varying the temperature; it possesses a faster response at temperatures above the melting point of the -S-(CH2)(11)OH moiety.