<p>The current global supply of a range of critical metals such as bismuth (Bi), gallium (Ga), indium (In), and tellurium (Te) is predominantly dependent on their production as a co- or by-product of the extraction of other more major commodities from a range of precious and base metal mineral deposits. Porphyry copper–molybdenum deposits (PCDs) supply the majority or significant amounts of global annual Cu, Mo, and Au production although the potential by-product recovery of bismuth, gallium, indium, and tellurium from most of these globally important deposits has not been extensively studied. The Río Blanco PCD in Central Chile hosts significant copper and molybdenum resources and reserves but the critical co- and by-product potential of this deposit remains relatively unassessed. This study investigates the trace element concentrations of bismuth, gallium, indium, and tellurium within the three sectors of the deposit, namely Don Luis, Río Blanco, and Sur-Sur. Statistical analysis of over approximately 10,000 multi-element inductively coupled plasma-mass spectrometry (ICP-MS) data from diamond core drill holes yields a strong correlation between bismuth and tellurium (<i>r</i> = 0.78), with tellurium enriched in some samples to levels of 300 times average crustal abundance. A proxy-based approach was used to estimate the hidden bismuth, gallium, indium, and tellurium inventory within these three deposits. This analysis suggests significant amounts of unassessed potential critical metal production within the known Río Blanco PCD. Applying this knowledge to assess existing PCDs’ recovery potential can add significant economic and sustainability value to current operations. Furthermore, the determination of the co- and by-product potential of these mineral systems is a key step in enhancing the security of supply for these critical metals that are vital for both modern life and the global energy transition.</p>