β-Cyclodextrin, a robust organocatalyst has been explored for the straightforward and facile synthesis of tetrazolo[1,2a]pyrimidine and [1,2,4]triazolo[1,5-a]pyrimidine derivatives through one-pot three-component tandem annulations reaction under solvent-free condition using aldehyde, active methylene compound and 5-aminotetrazole or 3-amino-1,2,4-triazole respectively. This greener chemical procedure has advantages such as shorter reaction time, absence of toxic and hazardous catalyst, chemicals and solvent, highly functional group tolerance, easy work up procedure and product separation.