Leaf area index (LAI) is a key biophysical variable fundamental in natural vegetation and agricultural land monitoring and modelling studies. This paper is aimed at comparing, validating and discussing different LAI satellite products from operational services and customized solution based on innovative Earth Observation (EO) data such as Landsat-7⁄8 and Sentinel-2A. The comparison was performed to assess overall quality of LAI estimates for rice, as a fundamental input of different scale (regional to local) operational crop monitoring systems such as the ones developed during the “An Earth obseRvation Model based RicE information Service” (ERMES) project. We adopted a multiscale approach following international recognized protocols of the Committee on Earth Observation Satellites (CEOS) Land Product Validation (LPV) guidelines in different steps: (1) acquisition of representative field sample measurements, (2) validation of decametric satellite product (10–30 m spatial resolution), and (3) exploitation of such data to assess quality of medium-resolution operational products (~1000 m). The study areas were located in the main European rice areas in Spain, Italy and Greece. Field campaigns were conducted during three entire rice seasons (2014, 2015 and 2016—from sowing to full-flowering) to acquire multi-temporal ground LAI measurements and to assess Landsat-7⁄8 LAI estimates. Results highlighted good correspondence between Landsat-7⁄8 LAI estimates and ground measurements revealing high correlations (R2 ≥ 0.89) and low root mean squared errors (RMSE ≤ 0.75) in all seasons. Landsat-7⁄8 as well as Sentinel-2A high-resolution LAI retrievals, were compared with satellite LAI products operationally derived from MODIS (MOD15A2), Copernicus PROBA-V (GEOV1), and the recent EUMETSAT Polar System (EPS) LAI product. Good agreement was observed between high- and medium-resolution LAI estimates. In particular, the EPS LAI product was the most correlated product with both Landsat/7-8 and Sentinel-2A estimates, revealing R2 ≥ 0.93 and RMSE ≤ 0.53 m2/m2. In addition, a comparison exercise of EPS, GEOV1 and MODIS revealed high correlations (R2 ≥ 0.90) and RMSE ≤ 0.80 m2/m2 in all cases and years. The temporal assessment shows that the three satellite products capture well the seasonality during the crop phenological cycle. Discrepancies are observed mainly in absolute values retrieved for the peak of rice season. This is the first study that provides a quantitative assessment on the quality of available operational LAI product for rice monitoring to both the scientific community and users of agro-monitoring operational services.