Summary: We have synthesized novel coacervate‐droplet gels, which were applied to controlling the transportation of DNA in electrophoresis. Coacervate droplets are colloidal particles and they are usually composed of positive and negative polyelectrolytes. However, the polyzwitterion (polyampholyte) PDMAPS can form coacervate droplets in water by itself, since PDMAPS has both positive and negative charges in each side group of main chain. Coacervate droplets have a unique nature and can catch charged macromolecules such as DNA. In order to utilize the nature of the PDMAPS coacervate droplets for the catch and release of DNA, we stabilized PDMAPS droplets in gels. The droplets catch the DNA in electrophoresis and the release of DNA can be controlled by temperature and salt addition.Electrophoresis of DNA, using coacervate‐dispersed PAAm gels, prepared at various PDMAPS concentrations. The circles indicate the PAAm gels embedded in agarose gels.magnified imageElectrophoresis of DNA, using coacervate‐dispersed PAAm gels, prepared at various PDMAPS concentrations. The circles indicate the PAAm gels embedded in agarose gels.