In previous studies, parameters derived from polarimetric target decompositions have proven as very effective features for crop classification with single/multi-temporal polarimetric synthetic aperture radar (PolSAR) data. In particular, a classical eigenvalue-eigenvector-based decomposition approach named after Cloude–Pottier decomposition (or “H/A/α”) has been frequently used to construct classification approaches. A model-based decomposition approach proposed by Neumann some years ago provides two parameters with very similar physical meanings to polarimetric scattering entropy H and the alpha angle α in Cloude–Pottier decomposition. However, the main aim of the Neumann decomposition is to describe the morphological characteristics of vegetation. Therefore, it is worth investigating the performance of Neumann decomposition on crop classification, since vegetation is the principal type of targets in agricultural scenes. In this paper, a multi-temporal supervised classification method based on Neumann decomposition and Random Forest Classifier (named “ND-RF”) is proposed. The three parameters from Neumann decomposition, computed along the time series of data, are used as classification features. Finally, the Random Forest Classifier is applied for supervised classification. For comparison, an analogue classification scheme is constructed by replacing the Neumann decomposition with the Cloude–Pottier decomposition, hence named CP-RF. For validation, a time series of 11 polarimetric RADARSAT-2 SAR images acquired over an agricultural site in London, Ontario, Canada in 2015 is employed. Totally, 10 multi-temporal combinations of datasets were tested by adding images one by one sequentially along the SAR observation time. The results show that the ND-RF method generally produces better classification performance than the CP-RF method, with the largest improvement of over 12% in overall accuracy. Further tests show that the two parameters similar to entropy and alpha angle produce classification results close to those of CP-RF, whereas the third parameter in the Neumann decomposition is more effective in improving the classification accuracy with respect to the Cloude–Pottier decomposition.