In the present work, first, the reference catalyst super acidic nanostructured sulfated zirconia (SZ) and super acidic nanostructured aluminum chloride impregnated sulfated zirconium oxides in mole ratios of Zr4+:Al3+ as 2:1 (ACSZ-1), 1:1 (ACSZ-2), and 1:2 (ACSZ-3) were synthesized by a simple precipitation method. The catalytic performance of these four catalysts were evaluated during the isomerization of n-hexane, n-heptane, and n-octane to their corresponding branched chain isomers at low temperature and pressure conditions. ACSZ-2 shows high activity toward isomerization of n-hexane, n-heptane, and n-octane into their corresponding branched chain isomers. The reference catalyst SZ was proved to be less effective compare to the other three synthesized ACSZ catalysts. Ammonia-temperature-programmed desorption of these two materials ensures that the super acidity of ACSZ-2 is higher than that of SZ. Atomic force microscopic and scanning electron microscopic pictures predict the nature of the surface of the catalysts. Transmission electron micrographic analysis indicates the presence of particle-bulks having average size 12–20 nm, presenting an amorphous nature and having no definite surface morphology of ACSZ-2. Fourier transform infrared provides an outline regarding different linkages and bond connectivities between atoms and groups in ACSZ-2 and SZ. After catalyst evaluation and characterization a probable reaction mechanism has been proposed theoretically. The reactivity and selectivity of ACSZ-2 and SZ as well as the order and activation energy of the isomerization reactions in presence of ACSZ-2 have been calculated. The use of ACSZ-2 is beneficial from the point of cost efficiency as well as its use is energy saving. © 2017 Taylor & Francis.