Synthesis of perfluoromethanesulfonyl fluoride(PFMSF) which is a valuable precursor of perfluoro-chemicals such as surface modifier and fine chemicals was studied by electrochemical fluorination (ECF). In order to determine the termination of preelectrolysis, it was carried to monitor the variation of current during preelectrolysis by means of constant cell voltage operation. In a batch cell, chronopotentiometric electrolysis and various chemical analysis such as GC, GC/MS and If were used to understand the potential change of electrode and synthesis and control of hazardous gases products. Termination of preelectrolysis was determinated by measurement the current and/or detection of $F_2$ gas generation. And during the preelectrolysis, an amount of generated $OF_2$ was shown that a lot of moisture was absorbed from air when a cell was filled with anhydrous hydrogen fluoride( AHF ). Above 4V cell voltage, $F_2$ gas was generated and acted on any form of fluorinating agents. In the ECF of MSC (methane sulfonyl chloride) by constant current operation, the potential of anode was intimately relation with generation of $SO_2F_2$. Exchange of Cl to F was dominatly occured in a initial stage. There were various gaseous products including PFMSF as main product and $C_4$ compounds.