Globally, excessive copper (Cu) absorption in artificially reared calves may increase the risk of excessive hepatic Cu accumulation, likely driven by their elevated pre-ruminant absorptive capacity, with the potential for harmful Cu accumulation leading to adverse health and productivity outcomes. However, quantitative data across the weaning transition remains limited. This study utilized secondary data and bio-banked samples from 35 Holstein–Friesian bull calves to estimate hepatic Cu absorption coefficients pre- and post-weaning. Although mean hepatic Cu concentrations remained broadly stable throughout the study, between 311 and 675 mg/kg of DM, changes varied by developmental stage: calves experienced hepatic Cu accumulation of 2.47 mg of Cu/kg of DM/d pre-weaning but a net reduction of 1.79 mg/kg of DM/d post-weaning. Pre-weaning calves exhibited a hepatic Cu absorption coefficient of 81.1% compared to post-weaning calves, where the hepatic Cu absorption coefficient was 4.9%. This reduction in absorptive capacity is consistent with increased rumen development and greater antagonism from dietary sulfur and molybdenum. Balance-adjusted total dietary Cu requirements were estimated at 3.18 mg/kg of DM pre-weaning and 15.21 mg/kg of DM post-weaning. These findings demonstrate that the pre-weaning period represents a phase of high Cu absorption and heightened susceptibility to hepatic Cu accumulation, even when dietary Cu meets current recommendations. Refining Cu feeding guidelines to more accurately reflect developmental stage and rumen maturation may help prevent excessive hepatic Cu loading while maintaining adequate mineral supply.