Changing size and shape of zeolitic crystals brings about enhanced diffusion properties and related promotion of catalytic performances. This work puts forward a phase-transfer synthetic strategy to generate ATO nanocrystalline silicoaluminophosphates spheroids under tumbling crystallization using aluminum isopropoxide dissolved in toluene and other ingredients (fumed silica/phosphoric acid/Di-n-hexylamine) dissolved in water as precursors. Toluene and aqueous phase formed a Pickering emulsion like structure during hydrothermal crystallization. Highly uniform crystalline spheroids of weighted 55 nm with strong acidity and high surface area were obtained, which exhibited a high isomer yield up to 79% in n-heptane hydroisomerization. Comparisons of product distribution and kinetic studies suggest that monomethyl-branched isomer selectivity is controlled by product shape selectivity, whereas dimethylbranched isomer selectivity is affected by combined transition state and product shape selectivity. The increase in selectivity for ATO spheroids is attributed to an expansion of intrinsic reaction controlled temperature regime and an improved diffusion property. (C) 2018 Elsevier Inc. All rights reserved.