The highly specialized materials needed for the de-carbonization of energy, smart devices and the internet of things have created supply concerns of critical elements used in these applications. Several critical elements are produced as by-products from base metal mining and processing. Increasing the capture of critical elements from existing operations should lead to a more resilient and sustainable supply of these elements. Towards this goal, this paper presents a review of the distribution behavior of five critical elements (selenium, tellurium, arsenic, antimony and bismuth) through the primary copper pyrometallurgical supply chain. This review identifies gaps in the distribution/concentration data of these elements in deposits and during mineral processing. Smelter dusts, refinery slimes and electrolyte are points of enrichment that can be targeted for additional recovery of these elements. Using published data, copper smelter dusts appear to contain enough arsenic and bismuth to meet the world's supply needs. Industrial data collected from 29 refineries and represents ~46% of the world's electrorefining production was extrapolated to examine the contained annual content of these five elements. Copper anodes contain 7900 tonnes/yr of selenium, 2300 tonnes/yr of tellurium, 24,000 tonnes/yr arsenic, 7100 tonnes/yr of antimony and 5100 tonnes/yr of bismuth. The selenium and tellurium contents are 2-3 times and 4-5 times more than the current world's annual production of these elements, respectively. While technology development in the processing of smelter dusts and refinery slimes could provide important breakthroughs, government and corporate collaboration are likely needed to encourage increased recovery of selenium, tellurium, arsenic, antimony and bismuth from the primary copper pyrometallurgical supply chain.