The present method of forming a nitride semiconductor epitaxial layer includes the steps of growing at least one layer of nitride semiconductor epitaxial layer on a nitride semiconductor substrate having a dislocation density lower than or equal to 1×107 cm−2 with a chemical decomposition layer interposed therebetween, the chemical decomposition layer being chemically decomposed at least with either a gas or an electrolytic solution, and decomposing the chemical decomposition layer at least with either the gas or the electrolytic solution at least either during or after the step of growing the nitride semiconductor epitaxial layer, thereby separating the nitride semiconductor epitaxial layer from the nitride semiconductor substrate. A high-quality nitride semiconductor epitaxial layer suffering less damage when separated from the nitride semiconductor substrate is thereby formed.