An extended grey relational analysis (GRA) method is introduced in this article to reduce the limitations of the classical GRA method using the cumulative prospect theory (CPT) which takes into account psychological factors such as the risk appetite of decision makers. Moreover, the circumstance of probabilistic hesitant fuzzy (PHF) which assigns probabilistic values to DMs’ different levels of hesitation shows its superiority when making decisions in a complex environment. Meanwhile the weighting vector of each attribute is calculated according to the entropy which is calculated by the different prospect decision elements. Thus, in this paper, we proposed an extended GRA method based on cumulative prospect theory in the probabilistic hesitant fuzzy circumstance and applying the model in the selection of the green supplier. At last, the comparative analysis and the simulation analysis are made to show the practicability of this newly proposed method.