Development of new microporous organic polymers attracts significant attention due to a wide scope of promising applications. In addition, the synthesis of soluble, non-crosslinking polymers of high surface area and uniform microporosity is very challenging, and the methods for soluble microporous polymers formation are rather limited. In this work, we report a new approach to construct porous polyphenylenes which employs the Diels–Alder polycondensation of multifunctional ethynyl-containing monomers of different spatial architecture with bis(cyclopentadienone)s. The resulting polymers were soluble in common organic solvents, and their structure and properties were assessed by NMR, TGA, DSC, and SEC studies. The polymers demonstrated a specific surface area up to 751 m2·g−1and ultramicroporous (pore size ≤ 0.6 nm) structure. N2and CO2adsorption–desorption data revealed that porosity parameters, e.g., specific surface area and pore sizes, can be tuned selectively by varying the type of monomers and reaction conditions.