A new view to determine concentration of dissolved acetylene in ambient temperature and pressure was put forward, and solubility of acetylene in different solvents was investigated by UV-Vis. (UV-Vis spectrophotometry). Influence of cosolvents such as acetone, TEG (triethylene glycol), DMSO (dimethyl sulfoxide), DMF (N,N-dimethyl formamide) especially the green cosolvent of TEG and its mechanism and volume fraction, temperature and scan rate on the process of electrochemical oxidation of acetylene at Pt electrode were examined by CV (cyclic voltammetry). The analysis results show that the concentration of dissolved acetylene can be determined accurately through claret-colored copper acetylide by UV-Vis. (at 542 nm), the solubility order of acetylene in different solvents is DMF>DMSO>TEG>acetone, the hydrogen bonding interactions were identified as the main interaction controlling the mutual solubility of the H2O in Na2SO4 solution and TEG in the system, and when the supporting electrolyte is 0.5 mol·L-1 Na2SO4 with TEG (vol.9%), the dissolved acetylene can be the most easily oxidized by OH· from the electrolysis process of Na2SO4 solution and the ipa (anodic peak current) is maximum, the process of electrochemical oxidation of acetylene at Pd electrode is under adsorption control and irreversible, the Ea (apparent activation energy) of the process of electrochemical oxidation of acetylene at Pd electrode is 13.20 kJ·mol-1. This study expects to seek a kind of good solvent acetylene and provides theoretical basis and experimental guidance to the research of electrochemical oxidation acetylene process and the development of sensor for acetylene (especially electrochemical sensor for acetylene), green chemistry and acetylene chemical industry.