Emerging interest in designing multi-responsive soft materials for diverse applications leads to the development of system that is embedded with the functional groups with stimuli responsive character. Surface active ionic liquids (SAILs) with an ability to form various structural aggregates can form an interesting candidate in designing soft materials with stimuli-responsive character. Embedding photo-responsive moieties into SAILs with existing pH-responsive properties unlocks a broader range of potential uses. Herein, we have prepared the photo- and pH responsive catanionic giant vesicles (GV) through synergetic interaction between, pH responsive choline oleate ([Ch][Ol]) and photo-responsive (4-methyl-4-(2-(octyloxy)-2-oxoethyl) morpholin-4-ium(E)-4-((4-(dimethylamino) phenyl) diazenyl) benzenesulfonate ([C8EMorph][MO]). The photo responsiveness in the GV is introduced through [C8EMorph][MO], which shows E-Z isomerisation by 460 nm light irradiation, whereas the pH responsive character through [Ch][Ol]. We used absorbance measurement complimented with computational study to characterize the photo-responsive behaviour. Irradiating the GV with light of suitable wavelength and changing the pH of the system alters the behaviour of the aggregates. SANS analysis shows that, before irradiation, the size of bilayer thickness of GV was 28 Å and after irradiation it increased to 31 Å leads to increment in overall size of GV. This is due to the formation of Z-[C8EMorph][MO] after irradiation, which leads to alter the interactions slightly between the both SAILs. Also, the change in pH of vesicles causes the alteration in size and shape of vesicles confirmed through the SANS. Stability of the GVs in terms of temperature, dilution and time were also analyzed to characterize the GVs for practical applications. The insights gained from this study could be valuable for developing materials for these applications such as probes, cargo carriers, and microreactors in future research.