Red-edge (RE) spectral vegetation indices (SVIs)—combining bands on the sharp change region between near infrared (NIR) and visible (VIS) bands—alongside with SVIs solely based on NIR-shoulder bands (wavelengths 750–900 nm) have been shown to perform well in estimating leaf area index (LAI) from proximal and remote sensors. In this work, we used RE and NIR-shoulder SVIs to assess the full potential of bands provided by Sentinel-2 (S-2) and Sentinel-3 (S-3) sensors at both temporal and spatial scales for grassland LAI estimations. Ground temporal and spatial observations of hyperspectral reflectance and LAI were carried out at two grassland sites (Monte Bondone, Italy, and Neustift, Austria). A strong correlation (R2 > 0.8) was observed between grassland LAI and both RE and NIR-shoulder SVIs on a temporal basis, but not on a spatial basis. Using the PROSAIL Radiative Transfer Model (RTM), we demonstrated that grassland structural heterogeneity strongly affects the ability to retrieve LAI, with high uncertainties due to structural and biochemical PTs co-variation. The RENDVI783.740 SVI was the least affected by traits co-variation, and more studies are needed to confirm its potential for heterogeneous grasslands LAI monitoring using S-2, S-3, or Gaofen-5 (GF-5) and PRISMA bands.