The tailored synthesis of periodic coordination structures is fundamentally important for the design of porous compounds with desired functionalities. The building block approach allows a rational and modular design of metal-organic frameworks to be accomplished from the scratch. This concept takes the advantage of the structural robustness and fixed geometry of ligands in the pre-synthesized complexes. Moreover, such a synthetic protocol can lead to otherwise unaccessible coordination structures. This review outlines the examples of the successful creation of metal-organic frameworks from discrete polynuclear complexes. We hope this work will inspire researchers in their everlasting quest for the targeted design of the materials with desired functionalities.