Three methods for preparing polyhedral oligomeric silsesquioxanes (POSS), which utilize the action of a base that can 
attack silicon atoms or anything that can react with protic solvents (such as ROH, H2O, etc.) and produce hydroxides [  OH]-, 
alkoxide [RO]- and other compounds.  The first method uses these bases to effectively redistribute the 
silicon-
oxygen skeleton structure in the polymerized 
silsesquioxane [RSiO1.5]∞ to become a POSS 
nanostructure, that is, the formula [(RSiO1.5)n]∑  Homoleptic fragments represented by #, functionalized homoleptic fragments represented by [(RXSiO1.5)n]∑#, 
hybrid compounds represented by [(RSiO1.5)m(R'SiO1.5)n]∑#  fragments (heteroleptic) and functionalized heterosegment nanostructures represented by {(RSiO1.5)m(RXSiO1.0)n}∑#, where ∞=1-1,000,000 or higher.  The second method uses a base to help form POSS nanostructures from the 
silane RSiX3 and the linear or cyclic 
silsesquioxane represented by the formula RX2Si-(OSiRX)m-OSiRX2, that is, the formula [(RSiO1.5)n  ]∑#, the homogeneous fragments shown and the miscellaneous fragments shown in [(RSiO1.5)m(R'SiO1.5)n]∑# and the heterogeneous fragments shown in [(RSiO1.5)m(RXSiO1.0)n]∑#  Functionalized heterosegment 
nanostructure, where m=0-10, X=OH, Cl, Br, I, 
alkoxide OR, acetate OOCR, 
peroxide OOR, amine NR2, 
isocyanate NCO and R.  The third method uses alkali to selectively open the 
silicon-
oxygen-silicon (Si-O-Si) bonds in the POSS structure to form POSS species with incompletely condensed nanostructures.  These methods also provide stereochemical control of X.  These three methods can generate new POSS species, which can ultimately be transformed into POSS species suitable for 
polymerization, 
grafting, or other desired chemical reactions through additional 
chemical control.