A simple method was developed to. realize a self-assembled block copolymer (BCP) lamellar microdomain morphology with a full pitch of 5.4 nm through an acid hydrolysis of poly(solketal methacrylate-b-styrene) (PSM-b-PS). The acid hydrolysis transforms PSM-b-PS, having two hydrophobic blocks, into poly(glycerol monomethacrylate-b-styrene) (PGM-b-PS), having one hydrophilic and one hydrophobic block. This transformation markedly increases the segmental interaction parameter such that a phase-mixed PSM-b-PS can be transformed in the solid state into a microphase-separated BCP without the use of any additives. Correlation hole scattering of the PSM-b-PS in the phase mixed state yields a segmental interaction parameter (x) given by x = 0.0196 + 4.694/T, where T is the absolute temperature. With the symmetric BCPs used in this study, the ordered lamellar microdomain pitch was determined by small-angle X-ray scattering (SAXS) as a function of the degree of polymerization (16 <= N <= 1246). For the lamellar microdomains of PGM-b-PS, the scattering profiles show many higher order reflections with an increase in the domain spacing (L-0). The lowest molar mass sample (M-n = 2200 g/mol, N = 16) had sub-3 nm microdomains after conversion to PGM-b-PS.