An improved domino/Knoevenagel-hetero-Diels-Alder reaction of two new aldehyde substrates; 7-olefinoxy-coumarin-8-carbaldehyde and 2-alkensulfanyl-quinoline-3-carbaldehyde, with pyrazolones was studied in ionic liquid triethylammonium acetate (TEAA), affording a series of pyrazolopyran annulated-pyrano-fused coumarins, and thiopyrano-fused quinolones. Besides acting as catalyst, since no additional catalyst used, the ionic liquid TEAA also promised its easy recovery. In all new polyheterocycles, the cis-fusion of two pyranyl rings had been inferred from 2D NMR COSY and NOESY experiments. All are good antitubercular agents, as they are found active against Mycobacterium tuberculosis H37Rv, and antibacterial agents, as they are found active against three Gram-positive (Streptococcus pneumoniae, Clostridium tetani, Bacillus subtilis) and three Gram-negative (Salmonella typhi, Vibrio cholerae, Escherichia coli) bacteria.