The alcohol solvent can effectively regulate the electrochemical property of Ni-Co LDH. In this study, the aqueous solutions of lower monohydric alcohols were used to synthesize Ni-Co LDH using the solvothermal method, and the effects of alcohol type and content on the electrochemical performance of Ni-Co LDH were investigated. The ab initio calculation and characterization analysis were performed to elucidate the mechanism of how coordination of alcohol molecules regulates the nucleation and growth of materials at the micro-level. The electrochemical property of the battery-type Ni-Co LDH is improved by optimizing the molar ratio of Ni to Co. The causes of the specific capacity decay of Ni-Co LDHs are also explored by electron microscopy and spectroscopy. Finally, a button supercapacitor with high energy density has been assembled, in which activated carbon (AC) is the negative material, and Ni-Co LDH is the positive material. This study provides some insights into controllable preparation of Ni-Co LDHs as alternative materials for SCs.