The invention provides a preparation method of a phosphooxyl indole compound and a derivative thereof. The preparation method comprises the following steps: weighing 1eq of a diazo indole compound and dissolving into an organic solvent so as to obtain a diazo solution with the concentration of 0.3mol/L to 0.5mol/L; adding 1eq to 1.2eq of a phosphooxyl compound and 0.05eq to 0.10eq of acetonitrile copper hexafluorophosphate into a flask and adding an organic solvent, wherein the concentration of the phosphooxyl compound in the solution is 0.3mol/L to 0.5mol/L; slowly dropwise adding the diazo solution into a round bottomed flask and reacting to obtain a crude product; carrying out column chromatography on the crude product by utilizing a solution containing ethyl acetate and petroleum ether at the volume ratio of (6 to 3) to 1, so as to obtain the phosphooxyl indole compound and the derivative thereof. According to the preparation method, a route of directly constructing a C(sp2)-P bond by adopting metal catalysis in one step is adopted; reaction conditions are moderate and gram-scale reaction can be realized; a series of phosphooxyl indole compound derivatives can be rapidly and simply synthesized and diversified compound frameworks are provided; the preparation method has very great meanings on new drug screening and pharmaceutical manufacturing processes.