Chlorophyll content at leaf level is an important variable because of its crucial role in photosynthesis and in understanding plant functioning. In this study, we tested the hypothesis that the ratio of a vegetation index (VI) for estimating canopy chlorophyll content (CCC) and one for estimating leaf area index (LAI) can be used to derive chlorophyll content at the leaf level. This hypothesis for estimating chlorophyll content at the leaf level was tested using simulations with the PROSAIL radiative transfer model and field spectroradiometry measurements in five consecutive years (2010–2014) for potato crops on experimental fields. During the growing season, in-situ field measurements of LAI and leaf chlorophyll content (LCC) were performed. Results showed that good estimates of LCC were feasible using ratio vegetation indices (VIs). This was tested at satellite level using RapidEye images. This letter presents a proof of concept for estimating LCC using Sentinel-2 data. Results confirm the importance of the red-edge bands for agricultural applications, but also showed that indices using the red-edge bands may be replaced by indices using green bands. It should now be tested with real Sentinel-2 data whether its spectral bands at 10 m spatial resolution are suitable for estimating LCC, avoiding the need for red-edge bands that only are available at 20 m.