This article provides an overview of the results of 10-year (2008–2018) studies on the structure and properties of furans and their benzo derivatives. Particular attention is paid to strategies to improve stability of furan-containing systems by introducing p-block inorganic elements and by furan annelation with other conjugated aromatic systems. We also show that furans and benzofurans represent advantageous alternatives to thiophenes and thiophene-based building units toward the design and synthesis of novel “green” polymeric materials with desired properties for optoelectronic applications.