Tetrathiafulvalene (TTF) and its numerous derivatives are among the most versatile electroactive organic molecules due to their remarkable redox properties, their use as building blocks for the development of molecular conductors, and diverse applications in organic electronics. TTF derivatives have also been widely explored as molecular switches, sensors, rectifiers, transistors, and for nonlinear optics, among other uses. More recently and since the pioneering study reporting the palladium-catalysed direct C-H arylation, tetraarylated TTFs have been employed for the construction of functional porous frameworks such as Metal-Organic Frameworks (MOFs), Covalent Organic Frameworks (COFs) or Hydrogen-bonded Organic Frameworks (HOFs). However, direct C-H arylation has been limited to TTF derivatives, and the catalytic peripheral modification of other π-extended TTF cores is encouraged for the construction of electroactive frameworks exhibiting new electronic properties and functions.