We report a green, efficient and straightforward approach for the regioselective synthesis of new spiro-heterocyclic scaffolds using environmentally benevolent activated alumina balls (3-5 mm diameter) as a catalyst under neat reaction conditions. The methodology is advantageous because of its short reaction time, moderate to excellent yields, easy work-up, practical simplicity and high regioselectivity without any troublesome/hazardous disposal of the catalyst or toxic byproducts. The pore size of the catalyst plays a key role in the formation of the spiro derivatives. Specifically, we observed that the reaction yield was hardly affected by the surface area or pore volume, but surprisingly, the yield correlated directly with the pore size of the catalyst. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.