Microelectronics device performance and its reliability are directly related to and controlled by its constituent materials and their microstructure. Specific processes used to form and shape the materials microstructure need to be controlled in order to achieve the ultimate device performance. Examples of front-end and back-end ULSI processes, packaging process, and novel optical storage materials are given to illustrate such process-structure-property-reliability relationship. As more novel materials are introduced to meet the new requirements for device shrinkage, such under-standing is indispensable for future generation process development and reliability assessment.