Stable isotope values and radiocarbon ages were determined for pedogenic carbonate microsamples from relict soils and palaeosols from the Rio Grande Rift region of New Mexico. Carbonate nodules and clusters were sampled from fluvial and piedmont soils and palaeosols with widely varying exposure durations (7–900 ky). Pedogenic carbonates from individual soils exhibited irregular relationships between age and depth, ranging in radiocarbon age by ≤13 ky at individual depths. δ¹⁸O values, and to a lesser extent δ¹³C values, likewise had wide ranges within soils. However, comparing the stable isotope values of carbonates with similar radiocarbon ages, within and between soils, revealed consistent trends in stable isotope values over time. δ¹⁸O values of pedogenic carbonates tended to decrease with decreasing age 25–17 radiocarbon ka, and increased with decreasing age <15 radiocarbon ka, with a marked shift to more positive values at 9–6 ka. Pedogenic carbonates from the piedmont soils showed minimal variation in δ¹³C values with either depth or age, although the oldest palaeosol piedmont carbonates (radiocarbon ages of 24.5–19.2 ka) are ≥1‰ more negative than the younger piedmont palaeosol carbonates. Pedogenic carbonates in the relict fluvial soil, which has by far the longest exposure period, showed the greatest range in δ¹³C values. Comparing the δ¹³C values of samples of similar radiocarbon age from the relict fluvial soil indicates a transition from a mixed C₃:C₄ ecosystem at ∼11 ka to an effectively pure C₃ ecosystem at ∼9 ka, followed by a return to mixed vegetation by ∼5 ka. Thus, although C₄ vegetation persisted in southern New Mexico through the last glaciation, drought-resistant C₃ vegetation became dominant at ∼9 ka, prior to significant strengthening of the summer monsoon. This study illustrates that the stable isotope values of carbonate nodules and clusters from relict soils and/or slowly buried palaeosols can be used for palaeoenvironmental reconstructions in the context of a detailed chronologic framework.