Limited understanding of carbon dioxide sinks and sources on land is often linked to the inability to distinguish between the carbon dioxide taken up by photosynthesis, and that released by respiration. Carbonyl sulphide, a sulphur-containing analogue of carbon dioxide, is also taken up by plants, and could potentially serve as a powerful proxy for photosynthetic carbon dioxide uptake, which cannot be directly measured above the leaf scale. Indeed, variations in atmospheric concentrations of carbonyl sulphide are closely related to those of carbon dioxide at regional, local and leaf scales. Here, we use eddy covariance and laser spectroscopy to estimate the net exchange of carbon dioxide and carbonyl sulphide across three pine forests, a cotton field and a wheat field in Israel. We estimate gross primary productivity--a measure of ecosystem photosynthesis--directly from the carbonyl sulphide fluxes, and indirectly from carbon dioxide fluxes. The two estimates agree within an error of +/-15%. The ratio of carbonyl sulphide to carbon dioxide flux at the ecosystem scale was consistent with the variability in mixing ratios observed on seasonal timescales in the background atmosphere. We suggest that atmospheric measurements of carbonyl sulphide flux could provide an independent constraint on estimates of gross primary productivity, key to projecting the response of the land biosphere to climate change.