In recent years, hydrogels have found applications in a number of fields. One area where hydrogels have been extremely influential is biomedical applications. Hydrogels can be utilized in cell and drug delivery systems, tissue engineering matrices, and as absorbers of toxins. Hollow-structure hydrogels are especially attractive in drug delivery applications due to their faster diffusion dynamics and the capability to encapsulate greater amounts of drugs. Hydrogels can also be composed of DNA and due to the biological origin of DNA, these hydrogels are biocompatible and biodegradable, an aspect that can be challenging for synthetic hydrogels. In this work, we fabricated hollow-structure DNA hydrogels through electrospray ionization in combination with a bath solution containing bicine and aluminum ions (Al3+). We then optimized the DNA concentration and bath solution to produce hollow-structure hydrogels with minimal shape deformation. Afterwards, we fabricated hollow-structure DNA hydrogels that contained particles of interest and hollow-structure hydrogels composed of predominately carbon nanotubes. Lastly, we attempted to encapsulate particles of interest through the usage of a coaxial needle. The results from this work provide a preliminary investigation into the fabrication of hollow-structure DNA hydrogels and motivation for further study into hollow-structure DNA hydrogels.