The choice of reaction medium had a major influence on the micro-morphology, surface area and pore volume. The 18 hydrogen-substituted graphynes (HsGYs) were synthesized with various deep eutectic solvents (DESs) as the reaction medium by coupling polymerization. The results showed that DESs had the great influence on the morphology of HsGYs. Meanwhile, HsGYs with larger surface area can be obtained by using DESs with low density and hydrophobicity as the solvent. The structure and properties of materials were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectrometer, X-ray diffractomer, UV–Vis DRS spectrum, etc. The electrochemical and adsorption properties of samples with different morphologies were tested and analyzed. The cyclic voltammetry curves showed that the samples had good capacitance behavior. HsGY-1 and HsGY-3 had relatively small contact resistance through electrochemical impedance spectroscopy analysis. The adsorption experiments showed that HsGY-12 and HsGY-13, with the larger specific surface area (336.229 and 325.005 m2g−1), had the strongest adsorption performance to chrysophanol acid (28.5 and 29.2 mg g−1). By studying the influence of DESs as a reaction solvent on the properties of HsGYs, such as morphology and specific surface area, which provided reference for the synthesis method of polymers and its application in the fields of energy storage, separation analysis and gas adsorption.