Porous framework materials, including metal-organic frameworks (MOFs), are highly tunable materials with myriad potential applications ranging from chemical separations to gas storage to catalysis. This is due to the unusual local environment offered by their pores. Herein we will discuss how this tunability can be used to unlock new reactive species relevant to organic synthesis and catalysis, focusing on fluorination chemistry, which is critical to the pharmaceutical, polymer, and agrochemical industries. We will also draw inspiration from organic chemistry for the design of new chemical separations and electrocatalytically active materials.