The speciation analysis of arsenic has consistently been a subject of great interest. However, it remains challenging to analyze complex matrix samples that contain both arsenic and interfering components. In this case, it can be hard to choose the right combinations of different instrumental methods, or a separation method followed by detection, which is usually done using a spectral approach (hybrid methods). In the production control of copper electrorefining, the determination of the concentration of As (III) and As (V) helps to improve the quality of the cathode copper produced. This work investigated the possibility of directly determining both arsenic forms and total As in an electrolyte bath using ion chromatography (IC) with conductometric detection. The use of the ion chromatographic approach for the determination of As(V) in complex matrix samples such as copper electrolyte must take into account the presence of potential interferences from anions such as sulphates, sulfites, selenites, selenates, etc. The results revealed that the method is accurate and precise, with As(V) quantification limits of 15 µg.L-1 and detection limits of 5 µg.L-1. This method is suitable for assessing various types of arsenic in the production of electrolytic copper, with the aim of replacing the current technique that requires liquid-liquid extraction and ICP-OES detection. This led to the following improvements: Enhanced efficiency: The method eliminates the need for extensive and time-consuming sample preparation for the initial separation of arsenic forms. At the same time, the method's characteristics are comparable to those of ICP-OES with liquid-liquid extraction, which is often used in the speciation analysis of arsenic. The method is environmentally friendly as it avoids the use of organic and poisonous extractants. The method can simultaneously analyze other anions (PO43-, SO42-, F-, Cl-, etc.) with arsenates with appropriate calibration.