The present invention discloses a method for lift-off of an LED substrate. By eroding the sidewall of a GaN epitaxial layer, cavity structures are formed, which may act in cooperation with a non-fully filled patterned sapphire substrate from epitaxial growth to cause the GaN epitaxial layer to separate from the sapphire substrate. The method according to an embodiment of the present invention can effectively reduce the dislocation density in the growth of a GaN-based epitaxial layer; improve lattice quality, and realize rapid lift-off of an LED substrate, and has the advantages including low cost, no internal damage to the GaN film, elevated performance of the photoelectric device and improved luminous efficiency.