A gate structure of a non-volatile memory device and a method of forming the same including a tunnel oxide layer pattern, a charge trap layer pattern, a blocking dielectric layer pattern having the uppermost layer including a material having a first dielectric constant greater than that of a material included in the tunnel oxide layer pattern, and first and second conductive layer patterns. The gate structure includes a first spacer to cover at least the sidewall of the second conductive layer pattern. The gate structure includes a second spacer covering the sidewall of the first spacer and the sidewall of the first conductive layer pattern and including a material having a second dielectric constant equal to or greater than the first dielectric constant. In the non-volatile memory device including the gate structure, erase saturation caused by back tunneling is reduced.