An effective and economical copper-catalyzed approach for the synthesis of phosphorylated 1H-isochromenes is reported. This method is the first example of focus on ketone phosphonylation to establish a C-P bond and 6-endo-dig cyclization to construct a C-O bond between aryl- and alkyl-substituted alkynylketones and H-phosphinate esters, H-phosphites, and H-phosphine oxides, resulting in chemo- and regioselective phosphorylated 1H-isochromenes with moderate to excellent yields under smooth reaction conditions.