Automotive electrification holds the promise of mitigating transportation-related greenhouse gas (GHG) emissions, yet at the expense of growing demand for critical metals. Here, we analyze the trade-off between the decarbonization potential of the road transportation sector and its critical metal requirement from the demand-side perspective in 48 major countries committing to decarbonize their road transportation sectors aided by electric vehicles (EVs). Our results demonstrate that deploying EVs with 40–100% penetration by 2050 can increase lithium, nickel, cobalt, and manganese demands by 2909–7513%, 2127–5426%, 1039–2684%, and 1099–2838%, respectively, and grow platinum group metal requirement by 131–179% in the 48 investigated countries, relative to 2020. Higher EV penetration reduces GHG emissions from fuel use regardless of the transportation energy transition, while those from fuel production are more sensitive to energy-sector decarbonization and could reach nearly “net zero” by 2040.