Polyphenylene dendrimers (PPDs) are macromolecules distinguished by their highly branched 3D globular structures. PPDs are generally constructed around a central multi-functional core molecule with branches having phenyl moieties and end groups. PPDs consist of rigid, shape-persistent phenyl rings offering physicochemically stable and robust structures. Although these characteristic features make PPDs promising compounds to be used in many applications such as light harvesting, organic electronics, and catalysts, their gas and energy storage usage is limited due to their non-porous structure in the solid state. This thesis aims to take a novel modular approach to incorporate functional PPDs into porous dendritic polymers (PDendPs), which is accomplished by polymerizing 'shape-persistent dendrimers' with organic linkers. Using shape-persistent PPDs as monomers offers a local order in PDendPs, improving the predictability and controllability of their surface area and porosity. In this regard, this approach allows precise molecular control over structure and functionality in PDendPs. This thesis proposed polymerizing three generations of PPDs using a ditopic linker to prepare three different PDendPs. Therefore, three generations of PPDs having bromo atoms at the periphery were synthesized, and these PPDs were polymerized using 1,4-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzene as linker via Suzuki coupling reactions. PDendPs and PPDs have been characterized using various analytical techniques, including NMR, FT-IR, BET, TGA, XRD, SEM, and EDX. All synthesized polymers were exposed to ethanol vapor in order to investigate PDendPs' potential as a sensing material for chemiresistor sensor applications. Computational simulations were exploited to reinforce outcomes in wet-lab media.