Nitrogen-rich porous materials have outstanding gas sorption and separation capacity. Using cage amines in the synthesis of metal-organic frameworks is a simple approach for generating the free nitrogen donor centers within the channels of porous materials without the post-synthetic modification. 1,4-Diazabicyclo[2.2.2]octane has a linear arrangement of nitrogen centers and can be used as a linear linker for the design of porous MOF materials. Urotropine has four nitrogen atoms and can act as a tetrahedral four-connected, pyramidal three-connected or bent two-connected linker. Such a diversity of coordination possibilities enriches the structural chemistry of MOFs and allows obtaining the frameworks with unique secondary building units and topology. The presence of cage amines in the structure affects the sorption characteristics of the materials. They demonstrate high selectivity to CO2 and can participate as a heterogeneous base catalyst in the organic reactions. Besides that the cage-amine based metal-organic frameworks demonstrate photoluminescent properties and can be used as nanoreactors for photochemical transformations. These compounds are also an important object of thermodynamic studies helping us better understand the nature of host-guest interaction in the supramolecular systems.