Graphical abstract Highlights • New germanosilicate AFI has been hydrothermally synthesized. • Different characterization techniques reveal the incorporation of Al into the framework of germanosilicate AFI. • deGe-Al-AFI shows high toluene conversion and p -cymene selectivity for alkylation of toluene with isopropanol alcohol. Abstract A new germanosilicate structural analogue of AFI zeolite (Ge-AFI) was hydrothermally synthesized. One- and two-step alumination of the Ge-AFI zeolites were used to modify their structure and acidic properties traced using XRD, N 2 adsorption, ICP-OES, 27Al NMR, and FTIR spectroscopy. Two-step aluminated sample (deGe-Al-AFI) provided a higher Al content, stronger acid sites and a higher micropore volume than one-step aluminated sample (Al-AFI). Extensive evaluation of the catalytic performance of these AFI zeolites compared with reference conventional zeolite catalysts for alkylation of toluene with isopropyl alcohol showed that deGe-Al-AFI exhibited relatively high toluene conversion and selectivity to valuable p -cymene due to the optimized textural and acidic properties. [ABSTRACT FROM AUTHOR]