A comparison of the sensitivity of several broad- and narrow-band vegetation indices (VIs) to leaf chlorophyll content in planophile crop canopies is addressed by the analysis of a large synthetic dataset. Broad-band indices included classical slope-based VIs (i.e. NDVI—normalized difference VI and SR—simple ratio) and some indices incorporating green reflectance (i.e. Green NDVI, NIR/green ratio and the newly proposed CVI—chlorophyll vegetation index), whereas narrow-band indices included those specifically proposed to estimate leaf chlorophyll at the canopy scale (i.e. MCARI—modified chlorophyll absorption reflectance index, TCARI—transformed CARI, TCARI/OSAVI ratio—TCARI/optimized soil adjusted VI and REIP—red edge inflection position). Synthetic data were obtained from the coupled PROSPECT + SAILH leaf and canopy reflectance models in the direct mode. In addition to traditional regression-based statistics (coefficient of determination and root mean square error, RMSE), changes in sensitivity of a VI over the range of chlorophyll content were analyzed using a sensitivity function. The broad-band chlorophyll vegetation index outperformed the other VIs considered as a leaf chlorophyll estimator at the canopy scale, with the exception of the TCARI/OSAVI ratio for some soil conditions.