An interesting Rh(III)-catalyzed dual C-H functionalization/cyclization cascade of azomethine imine with diazophosphonate by a removable directing group for the synthesis of highly fused pyrano[de]isochromene has been achieved. The transformation shows that the desired pyrano[de]isochromenes with two oxygen atoms on its core scaffold could be constructed with good to excellent yields (up to 86%) via a facile one-pot, multiple-step cascade reaction, along with broad generality and versatility.