The synthesis of a series of new nine 3-benzoyl-2-benzylchromones is developed through a classical and an optimized Kostanecki–Robinson method involving an o-hydroxyphenyl-β- diketone and an acid anhydride. The different spectrokinetic studies carried out in solution and in polymer matrixes have highlighted the main structure/photochromic parameters relationships and the influence of the medium on the photochromic properties.