Di-, tri-, and tetrathienyl-substituted polycyclic aromatic fluorophores were prepared from different aryldi-, aryltri-, or aryltetrahalides by a simple and fast Suzuki coupling. The reaction was optimized for the synthesis of the desired materials on multigram scale. The coupled products were converted into the corresponding iodides through iodination with N-iodosuccinimide. The iodides turned out to be versatile starting materials for applications, such as periodic mesoporous organosilica syntheses. They were converted into a variety of new trimethoxysilyl arenes by using a very efficient Pd-mediated C-Si cross-coupling, which was also extended to the corresponding thienyl bromides by using a dimeric Pd(I) catalyst. All compounds were characterized by 1H NMR, 13C NMR, 29Si NMR, and ATR-IR spectroscopy and HRMS.