A new and convenient synthesis of aryl-substituted naphtho[2,1-a]azulenes by the combination of Suzuki-Miyaura, Sonogashira, and cycloisomerization reactions is reported. The methodology was applied to the synthesis of hitherto unknown azuleno[1,2-h]quinolines, cyclohepta[1,2]indeno[4,5-b]thiophenes, and cyclohepta[1,2]indeno[4,5-c]thiophenes. The impact of different fused-heterocyclic rings on the photophysical and electrochemical properties of these azulene derivatives was studied by experimental and theoretical methods and hence provides a rationale for the preparation of novel azulene derivatives with improved properties for application as organic materials.