A simple and efficient cascade synthesis was achieved to produce chloro substituted 9-phenyl-6H-benzo[c]chromenes under mild and additive-free reaction conditions via chlorination followed by benzannulation. This would be a green alternative approach to introduce a chlorine atom on poly hetero aromatic rings without use of other toxic and malodorous chlorinating agents. The core structure is a part of several biological active compounds, and this new protocol allows design of new polyheterocyclic frameworks using an alternative to traditional cross-coupling strategies.