Key leaf functional traits, such as chlorophyll and carotenoids content (Cab and Cxc), equivalent water thickness (EWT), and leaf mass per area (LMA), are essential to the characterization and monitoring of ecosystem function. Spectroscopy provides access to these four leaf traits by relying on their specific spectral absorptions over the 0.4–2.5 µm domain. In this study, we compare the performance of three categories of estimation methods to retrieve these four leaf traits from laboratory directional-hemispherical leaf reflectance and transmittance measurements: statistical, physical, and hybrid methods. To this aim, a dataset pooling samples from 114 deciduous and evergreen oak trees was collected on four sites in California (woodland savannas and mixed forests) over three seasons (spring, summer and fall) and was used to assess the performance of each method. Physical and hybrid methods were based on the PROSPECT leaf radiative transfer model. Physical methods included inversion of PROSPECT from iterative algorithms and look-up table (LUT)-based inversion. For LUT-based methods, two distance functions and two sampling schemes were tested. For statistical and hybrid methods, four distinct machine learning regression algorithms were compared: ridge, partial least squares regression (PLSR), Gaussian process regression (GPR), and random forest regression (RFR). In addition, we evaluated the transferability of statistical methods using an independent dataset (ANGERS Leaf optical properties database) to train the regression algorithms. Thus, a total of 17 estimations were compared. Firstly, we studied the PROSPECT leaf structural parameter N retrieved by iterative inversions and its distribution over our oak-specific dataset. N showed a more pronounced seasonal dependency for the deciduous species than for the evergreen species. For the four traits, the statistical methods trained on our dataset outperformed the PROSPECT-based methods. More particularly, statistical methods using GPR yielded the most accurate estimates (RMSE = 5.0 µg·cm−2; 1.3 µg·cm−2; 0.0009 cm; and 0.0009 g·cm−2 for Cab, Cxc, EWT, and LMA, respectively). Among the PROSPECT-based methods, the iterative inversion of this model led to the most accurate results for Cab, Cxc, and EWT (RMSE = 7.8 µg·cm−2; 2.0 µg·cm−2; and 0.0035 cm, respectively), while for LMA, a hybrid method with RFR (RMSE = 0.0030 g·cm−2) was the most accurate. These results showed that estimation accuracy is independent of the season. Considering the transferability of statistical methods, for the four leaf traits, estimation performance was inferior for estimators built on the ANGERS database compared to estimators built exclusively on our dataset. However, for EWT and LMA, we demonstrated that these types of statistical methods lead to better estimation accuracy than PROSPECT-based methods (RMSE = 0.0016 cm and 0.0013 g·cm−2 respectively). Finally, our results showed that more differences were observed between plant functional types than between species or seasons.