An efficient, simple and versatile synthesis of biologically valuable benzo[c]chromen-6-ones is achieved using a tandem photo-thermal-photo reaction sequence starting from 3,4-dichlorocoumarins and a 1,3-butadiene. In this concise one-pot protocol, neither metal catalyst nor peroxide promoter is needed and the products can be purified through simple recrystallization in most cases. The synthesis consists of a reaction sequence of photo-induced [4 + 2] and [2 + 2] cycloadditions, silica gel promoted elimination of HCl and electrocyclic cyclobutene ring opening followed by a photo-induced 6π electrocyclization. The reactions proceed well with a range of dichlorocoumarins and some typical butadienes to provide the corresponding annulated products in 70–80% yield.