4-Hydroxycoumarin (1) being endowed with both nucleophilic and electrophilic properties furnishes the dimeric coumarin derivative 3 in a pyridine catalyzed self-condensation process; while its attempted morpholine catalyzed self-condensation yields no dimeric coumarin derivative, but leads to the formation of the enamine derivative 2, establishing the existence of the less stable 2,4-chromandione tautomer (1′) of 4-hydroxycoumarin. Pyridine catalyzed condensation between 4-hydroxycoumarin and acrylic acid affords 4-salicyloylpimelic acid (4) via the formation of 3,3-disubstituted-4-hydroxycoumarin and its subsequent hydrolysis and decarboxylation. But the condensation under similar condition with crotonic acid and with mesityl oxide separately leads to the isolation of the pyranocoumarin derivatives 5 and 6, respectively, along with a little amount 3 in either case. However, when β,β-disubstituted-α,β-unsaturated acid like β,β-dimethylacrylic acid, and α,β-unsaturated acids with a bulky β-substitutent like cinnamic, p-chlorocinnamic and 3, 4-methylenedioxycinnamic acids are used, no condensation product excepting the same dimeric coumarin derivative 3 is formed apparently due to the reduced electrophilicity of the β-carbon and steric crowding in the transition state. Condensation of 4-hydroxycoumarin with ethyl acetoacetate produces the α-pyranocoumarin 7, while with acetylacetone leads to the formation of a novel bicyclo compound 8 having two 4-hydroxycoumarin moieties with one acetylacetone moiety bridging them. These condensations using other bases like sodium bicarbonate, piperidine and morpholine afford the same products with varied rates of their formation. Refluxing 4-hydroxycoumarin (1) or its enamine 2 with acetic anhydride in acetic acid gives 3-acetyl-2-hydroxy-4-chromanone (9), stabilized by intramolecular H-bonding and thus indicating the existence of the least stable tautomeric form 1″ (2-hydroxy-4-chromenone) of 4-hydroxycoumarin (1).