In this paper, we present a simple approach for the synthesis of well-defined macromolecules based on precisely isolated amino- and amido-functionalized octa T8 and deca T10 silsesquioxanes (SQs). Here, we show that reorganization of the siloxane cage-like core (T8 → T10) can be easily performed, including isolation of intermediates, and cage rearrangement achieved by using Brønsted superacid, trifluoromethanesulfonic acid (CF3SO3H). Moreover, T10-like SQs can be obtained in a one-step reaction by alkoxysilane condensation in trifluoromethanesulfonic acid conditions. The resulting decamers of amine-SQ and an amido-functionalized derivative containing long alkyl chains are reported for the first time in the literature. The non-fluorinated amido derivatives due to their lamellar-like nature and specific packing can serve as transparent hydrophobic coatings in various industrial applications. The obtained compounds were fully characterized using FT-IR, UV-vis, multinuclear NMR (1H, 13C, 29Si), DOSY NMR, TG-DTA, DSC, HR-MS, TEM, EDS and elemental analysis.