The highly soluble, perfect 2,5-dipropyl (alternate hydro- and benzo-) quinone-bridged ladder poly(methylsiloxane) (abbreviated as L) with molecular weight M-n = 1.9 x 10(4) was successfully synthesized for the first time through the supramolecular ladder assembly template (L') formed via the concerted effect of charge transfer (CT) interaction of quinone-hydroquinone (abbreviated as Q-HQ-CT) and silanol's H-bonding one of the hydrolates of monomers, 2,5-di[(3-dihydroxymethylsilyl)propyl]hydroquinone (M-1') and 2,5-di[(3-dihydroxymethylsilyl)propyl]benzoquinone (M-2'). The presence of perfect ladder structures of polymer L, in particular, ladder assembly L' very susceptible to ambient environment were well confirmed by the following data: (1) XRD analysis shows that L demonstrates two diffraction peaks representing the characteristic ladder width d(1) = 11.78 angstrom and the ladder thickness d(2) = 4.91 angstrom respectively, which are approximately consistent with the molecular simulation-based width d(1)' = 12.40 angstrom and thickness d(2)' = 5.40 angstrom. Similarly, solution XRD shows that L' also demonstrates the two peaks representing the width d(1) = 11.05 angstrom and the thickness d(2) = 4.61 angstrom, respectively, suggesting the presence of ladder structure of L'. (2) Si-29 NMR measurement gives the sharp peak with extremely small half peak width, W-hp< 1 ppm, of the moiety [=SiO2/2-] for either L or L'. (3) UV spectroscopy displays a new set of "red-shift" absorption peaks which are generated by CT interaction between M-1' and M-2' of L'. Moreover, there is the significant similarity of the peak fashions of L and L'. Meanwhile, fluorescence spectroscopy (FS) analysis shows emission peaks of L and L' are very alike. These results demonstrate that L' also has ladder structure. (4) In a series of control experiments, addition of H bond or CTC-blocking reagent (urea or HQ) to the solution of L' led to destruction of L' and great changes of the spectra of XRD, Si-29 NMR, UV, and FS. (5) As circumstantial evidence, DSC measurement gives a very high glass transition temperature (T-g = 137 degrees C), further indicating that L has a rigid rodlike skeleton without noticeable branches.