In this study, vinyl-terminated polysiloxane (abbreviated VISR) and allyl-terminated polysiloxane (abbreviated ALSR) were synthesized and characterized. The curing behaviors and viscoelastic and thermal properties of VISR/PHSR and ALSR/PHSR were comparatively investigated. DSC and in situ FT-IR spectroscopy can be adopted to study the influence of molecular structures on reactivity. The results prove that ALSR/PHSR shows higher reactivity including a higher reaction rate constant and cure degree than VISR/PHSR. Moreover, it is found that the Sestak-Berggren equation can adequately depict the cure kinetic model of silicone resin in hydrosilylation comparing the calculated results with experimental data. Additionally, DMA exhibits that the glass transition temperature and cross-linking density of ALSR/PHSR are much lower than those of VISR/PHSR, TGA data reveal that they have similar thermal stability as well as high char yield, and the decomposition energy ranges from 100 to 270 kJ/mol with increment of degree of mass conversion (alpha(d)) (alpha(d) = 0.15-0.85).