In this work a systematic investigation of crosslinking kinetics of Sylgard184 polydimethylsiloxane is performed in both isothermal and dynamic conditions. The results are discussed in terms of two conversions, αC and αR determined by thermal and rheological analysis, respectively. Thermal analysis can well detect the first stage of the reaction, while rheological analysis starts being sensitive only at longer time. However, once the rheological response is observable, it changes with time faster than the calorimetric one. From rheology experiments it comes out that the gel point occurs at αR = 0.53, independently of the applied thermal history. At gel point, αC is around 0.30 indicating that about 30% of the bonds involved in the crosslinking process is enough to create an infinite network. A modified version of the Kamal's autocatalytic model allows to fit and predict the experimental findings from both the techniques; however, two distinct sets of parameters have been used. The results of this work may be a useful tool to design appropriate curing cycles for the preparation of Sylgard184.