The aim of this paper is to demonstrate that spectral vegetation indices are good indicators of parameters describing the intensity of CO₂ exchange between crops and the atmosphere. Measurements were conducted over 2011-2013 on plots of an experimental arable station on winter wheat, winter rye, spring barley, and potatoes. CO2 fluxes were measured using the dynamic closed chamber system, while spectral vegetation indices were determined using SKYE multispectral sensors. Based on spectral data collected in 2011 and 2013, various models to estimate net ecosystem productivity and gross ecosystem productivity were developed. These models were then verified based on data collected in 2012. The R2 for the best model based on spectral data ranged from 0.71 to 0.83 and from 0.78 to 0.92, for net ecosystem productivity and gross ecosystem productivity, respectively. Such high R2 values indicate the utility of spectral vegetation indices in estimating CO₂ fluxes of crops. The effects of the soil background turned out to be an important factor decreasing the accuracy of the tested models.