Light-emitting diodes (LED) chip scale packages (CSPs) have been promoted as a new light source with many advantages in smaller package size, lower material and process cost, and better heat dissipation effect. However, as it is exposed in harsh environments such as high temperature, high humidity, and high blue light irradiation, silicone material used in LED CSPs always suffers deterioration, which will seriously affect the LED's reliability and working life. Thus, the preparation of high reliable silicone has practical significance to promote the application of LED CSPs in lighting. In this research, titanium was introduced into the molecular chain of phenyl silicone by using the hydrolysis condensation method. A high temperature aging test was then performed to the prepared silicone before and after modification, and their optical, thermomechanical, and dielectric properties were characterized to evaluate their reliabilities. The results show that: (1) the Arrhenius function with the dielectric property as an aging characterization can be used as a temperature accelerated life model to predict the service life of the prepared silicone and (2) the titanium modified silicone can advance the high temperature stability on optical properties, thermomechanical, and dielectric properties and enhance the life expectancy. The major contributions of this study are to support the improvement of the novel LED CSP packaging materials and processes, and also to provide the technical guidance on the fast, accurate, and cost-effective reliability assessment for high-quality LED light sources.