Data on aggregation/morphological behaviour of contrasting charge aqueous gemini mixtures at 303 K have been acquired in this study. Anionic and cationic components of the mixture were phosphoric acid, P, P' −1,4-butanedieyl, P, P' didodecylester, disodium salt (12–4-12A) and (ethane-1,2-diyl bis (N, N-dimethyl-N-alkylammoniumacetoamide) dichloride) (12-Eda-12 or 14-Eda-14), respectively. Fluorescence data are used to acquire critical micelle concentration (CMC) value and micro-environmental information (micro-polarity and dielectric constant). DLS, SANS and TEM confirm the presence of ellipsoidal, rod-shaped or vesicles at different compositions of the mixture(s). Further, zeta-potential (ζ) data reveal the charge reversal on the aggregate by mole fraction (x) variation (0–1) of the mixture. Solubilization of an anti-cancer drug (raloxifene hydrochloride, RLX) has been seen in various morphologies (spectrophotometrically) and it has been found that vesicles (formed at x = 0.4 or 0.6) solubilize more RLX than the any other morphology. RLX release profile follows Higuchi model which confirms the diffusional release mechanism. RLX solubilised in 12–4-12A + 14-Eda-14 mixture (x = 0.6 and x = 0.4, respectively) showed good cell proliferation behaviour (9.06 µg/mL) over pure RLX (21.75 µg/mL) towards MCF-7.