This study aimed to understand which vegetation indices (VIs) are an ideal proxy for describing phenology and interannual variability of Gross Primary Productivity (GPP) in short-rotation coppice (SRC) plantations. Canopy structure- and chlorophyll-sensitive VIs derived from Sentinel-2 images were used to estimate the start and end of the growing season (SOS and EOS, respectively) during the period 2016–2018, for an SRC poplar (Populus spp.) plantation in Lochristi (Belgium). Three different filtering methods (Savitzky–Golay (SavGol), polynomial (Polyfit) and Harmonic Analysis of Time Series (HANTS)) and five SOS- and EOS threshold methods (first derivative function, 10% and 20% percentages and 10% and 20% percentiles) were applied to identify the optimal methods for the determination of phenophases. Our results showed that the MEdium Resolution Imaging Spectrometer (MERIS) Terrestrial Chlorophyll Index (MTCI) had the best fit with GPP phenology, as derived from eddy covariance measurements, in identifying SOS- and EOS-dates. For SOS, the performance was only slightly better than for several other indices, whereas for EOS, MTCI performed markedly better. The relationship between SOS/EOS derived from GPP and VIs varied interannually. MTCI described best the seasonal pattern of the SRC plantation’s GPP (R2 = 0.52 when combining all three years). However, during the extreme dry year 2018, the Chlorophyll Red Edge Index performed slightly better in reproducing growing season GPP variability than MTCI (R2 = 0.59; R2 = 0.49, respectively). Regarding smoothing functions, Polyfit and HANTS methods showed the best (and very similar) performances. We further found that defining SOS as the date at which the 10% or 20% percentile occurred, yielded the best agreement between the VIs and the GPP; while for EOS the dates of the 10% percentile threshold came out as the best.