Electrical switching in CuxAs40Se60−x glasses has been studied over a wide composition range for 0≤x≤32. The glasses with lower Cu concentrations (x<15) do not exhibit switching, whereas glasses in the range 15≤x≤25 show a threshold type switching. The glasses in the range 26≤x≤29 exhibited an unusual switching from low‐resistance to high‐resistance state. For x≥30, the glasses are found to show a memory switching. The thermally crystallized samples indicate that the structural network is characterized by Cu3AsSe4 and As2Se3 for x<15 and by Cu3AsSe4 and Cu2As3 for x≥25. The composition range 15≤x≤20 is characterized only by Cu3AsSe4 structural units. The samples cooled from their melt show only the ternary Cu3AsSe4 for x≤20. For x>20, precipitates of “As” have also been observed along with Cu3AsSe4 and Cu2As3 phases. The present studies provided a unique way to understand the electrical switching exhibited by chalcogenide glasses based on the thermal model and the filament formation.