A method of forming a micropattern structure includes: coating a structure including a plurality of guide blocks extending in a first direction on a substrate and disposed to be spaced apart from each other in a second direction, which is perpendicular to the first direction, with a sacrificial material; ashing a portion of the sacrificial material to expose upper portions of the plurality of guide blocks; coating the structure with a first material having a polarity that is contrary to a polarity of a filling material filling the structure; heat-treating the structure to chemically bond the first material to the upper portions of the plurality of guide blocks; removing the sacrificial material and excess first material to form a first material cap chemically bonded to the upper portions of the plurality of guide blocks; and filling the structure with the filling material.