Sonochemical synthesis of nano-sized SrTiO3 carried out at close to room temperature, in ionic liquids (ILs) allows the tuning of particle size and particle morphology, that is, tracht and habitus, as well as particle aggregation via the choice of the ionic liquids (ILs) as the reaction medium. The nanoparticles demonstrate high performance for photocatalytic water splitting and photodecomposition of organic material. To this end bis(trifluoromethanesulfonyl)amide ([Tf2N](-))-based ILs with cations of different properties with respect to specific interactions with the target material are investigated. Isolated, 15 +/- 1 nm sized nano-spheres of SrTiO3 are observed to form in [C(3)mimOH][Tf2N] ([C(3)mimOH](+) = 1-(3-hydroxypropyl)-3-methylimidazolium). Aggregation of small sized nanoparticles are observed to around 250 +/- 100 nm large cube-like formations in [C(4)mim][Tf2N] ([C(4)mim](+) = 1-butyl-3-methylimidazolium), raspberry-like in [C4Py][Tf2N] ([C4Py](+) butylpyridinium), and ball-like in [P-66614][Tf2N] ([P-66614](+) tetradecyltrihexyl phosphonium). Importantly, the different materials show different performance as photocatalysts. SrTiO3 prepared in [C(4)mim][Tf2N] shows the highest photocatalytic activity for H-2 evolution (1115.4 mu mol h(-1)) when using 0.025 wt% Rh as the co-catalyst, whereas the material prepared in [C(3)mimOH][Tf2N] shows the highest activity for the photocatalytic degradation of methylene blue (88%) under UV irradiation. The different photocatalytic activities can be correlated with the different crystal surface facets expressed in the respective nanosized SrTiO3 material, {110} for material obtained from [C(4)mim][Tf2N], and {100} for material from [C(3)mimOH][Tf2N]. First-principles density functional theory (DFT) calculations are used to support the experimental findings.