There are complex interactions that take place during the adhesive coating process on siliconized liner at the silicone-adhesive interface. These silicone-adhesive interactions can differ based on adhesive and silicone technologies. This paper will look at how analytical techniques can be used to provide insights into the resulting release coating and how that coating impacts adhesive performance. Examples will be presented using a variety of analytical techniques such as rheology, spectroscopy and microscopy to understand various practical concern. The analytical data will be correlated to specific adhesive performance issues to show why and when various analytical techniques should (and should not be) used to solve critical quality and performance problems.