Measurements of atmospheric O2 and CO2 concentrations serve as a widely used means to partition global land and ocean carbon sinks. Interpretation of these measurements has assumed that the terrestrial biosphere contributes to changing O2 levels by either expanding or contracting in size, and thus serving as either a carbon sink or source (and conversely as either an oxygen source or sink). Here, we show how changes in atmospheric O2 can also occur if carbon within the terrestrial biosphere becomes more reduced or more oxidized, even with a constant carbon pool. At a global scale, we hypothesize that increasing levels of disturbance within many biomes has favored plant functional types with lower oxidative ratios and that this has caused carbon within the terrestrial biosphere to become increasingly more oxidized over a period of decades. Accounting for this mechanism in the global atmospheric O2 budget may require a small increase in the size of the land carbon sink. In a scenario based on the Carnegie–Ames–Stanford Approach model, a cumulative decrease in the oxidative ratio of net primary production (NPP) (moles of O2 produced per mole of CO2 fixed in NPP) by 0.01 over a period of 100 years would create an O2 disequilibrium of 0.0017 and require an increased land carbon sink of 0.1 Pg C yr−1 to balance global atmospheric O2 and CO2 budgets. At present, however, it is challenging to directly measure the oxidative ratio of terrestrial ecosystem exchange and even more difficult to detect a disequilibrium caused by a changing oxidative ratio of NPP. Information on plant and soil chemical composition complement gas exchange approaches for measuring the oxidative ratio, particularly for understanding how this quantity may respond to various global change processes over annual to decadal timescales.