We have reported a simple synthetic procedure based on Pdcatalysed direct C-H arylation to obtain a new family of DT-TTF derivatives bearing different functional groups (2-5). The electronic structure of DT-TTF can be modulated by introducing electron-withdrawing (2) or electron-donor (3) groups to decrease or increase the HOMO energy level, respectively, becoming very attractive for organic electronics. In addition, long-range ordered crystalline hydrogen-bonded networks of DT-TTF derivative 5 were observed at the graphite/liquid interface as revealed by STM studies. Interestingly, molecule 5 can reach a planar geometry on the graphite surface due to van der Waals interactions with the surface as well as H-bonding with neighbouring molecules, as supported by molecular models based on experimentally measured unit cell parameters. This work will also open the way to explore the design of new extended electroactive frameworks such as MOFs or COFs based on DT-TTF building blocks, being of great interest due to their promising electronic properties.