The customized processing of polymer materials in the microscale by high‐resolution 3D printing provides an easy access to advanced applications in the fields of optics, microfluidics, tissue engineering, and life science. However, the 3D printing of enclosed structures in the scale of tens of microns such as closed microfluidic channels remains a challenge as channel structures often are clogged by residual cured resin. Dual‐curing systems based on off‐stoichiometric thiol‐ene and thiol‐ene/epoxy chemistry are well‐known for adhesive‐free bonding in the fabrication of cast or injection molded microfluidic devices. Herein, the first high‐resolution stereolithography 3D printing of a dual‐curing thiol‐ene/epoxy system in the microscale for the fabrication of customized microfluidic devices is presented. In the first curing step, by high‐resolution 3D printing open microfluidic structures are produced. Consecutively, the microchannels are sealed by adhesive‐free dry bonding upon thermal initiation, producing well‐controlled structures with channel sizes down to 80 µm. Before bonding, the intermediate material allows for tailored surface modification with biotin, which allows for consecutive immobilization of various biomolecules. A DNA‐bioassay with specific patterning is shown in the sealed chip. The presented work paves the way toward the fabrication of customized microfluidic devices for a large range of specific bioassays.