Hexadecyltrimethylammonium bromide (CTAB) was utilized to template the growth of mesoporous silica particles via ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS) in the reaction solutions with varied volume fractions of ethanol (f(R)). The use of 9,10-bis(phenylethynyl) anthracene (BPEA) as a fluorescence probe unraveled a clear difference in interior structure between the CTAB micelles confined at different f(R). At f(R) of 0.3, the confined CTAB micelles consisting of regularly and densely packed alkane chains, which created crystalline interiors, in which the doped BPEA molecules were effectively isolated in the monomeric form and well protected against aggressive attack from the surrounding environment. At f(R) of 0.4 or 0.5, the confined CTAB micelles consisting of less regularly but densely packed alkane chains created glassy interiors, which enabled reversible aggregation of the doped BPEA in response to the surrounding environmental change, for instance, the ethanol content in the particle dispersion. At f(R) of 0.6 or 0.7, the confined CTAB micelles consisting of loosely packed alkane chains created amorphous interiors, which offered sufficiently large free spaces to facilitate the material exchange with the surrounding environment, as evidenced by noticeable intake of the Pyronin Y molecules present in the particle dispersion. The revealed phase modulation of the interiors of surfactant micelles, confined in the pores of mesoporous particles, from crystalline to glassy and amorphous structures, which were scarcely reported in literature, will inspire rational design of mesoporous silica particles with desired technical performance according to the purposes of the practical application.