Provided are a novel phosphinine oxide derivative and a preparation method thereof, and more specifically, the phosphinine oxide derivative includes an oxaphosphinine oxide derivative and an azaphosphinine oxide derivative.The phosphinine oxide derivative according to the present invention may have a pharmacological activity and a physiological activity, and may be used as a basic framework of a natural product and may be used for development of new drug and synthesis of various medical supplies.In addition, according to the preparation method of the phosphinine oxide derivative according to the present invention, various phosphinine oxide derivatives with a high yield may be prepared by a simple synthesis process using an intramolecular annulation between a phosphinic derivative and an alkyne derivative in the presence of a rhodium (Rh) catalyst or a ruthenium (Ru) catalyst and an oxidant.