School-enterprise cooperation plays a pivotal role in the cultivation of highly competent technical and skilled talents in vocational education. Enterprise masters, as primary participants in teaching within vocational institutions and major contributors to enterprise-based instruction, play a key role in improving the quality of technical and skilled talent training through their involvement in school-enterprise cooperation. This study utilizes non-random sampling methods to focus on selected enterprises in Jiangsu, Zhejiang, and Shanghai. By applying grounded theory, the study conducts step-by-step coding of interview transcripts from enterprise masters and constructs a model for the decision-making behaviors and influencing factors in school-enterprise cooperation. The research reveals that enterprise masters’ decision-making follows the intrinsic cyclical logic of “individual motivation—participation behaviors participation benefits..” Additionally, their decision-making is directly or indirectly influenced by key external factors such as “organizational motivation,” “master-apprentice interactions” and “student behavior”. To further promote enterprise masters’ participation in school-enterprise cooperation and improve the quality of talent training in vocational education, it is essential to standardize the training system and behavioral responsibilities of masters, deepen their role awareness and identity recognition, and establish stable role beliefs; strengthen the guidance and supervision of students’ career planning, establish communication and coordination mechanisms between schools and enterprises, and foster a harmonious master-apprentice relationship; and develop a multi-level incentive mechanism to protect masters’ vested interests and enhance their intrinsic motivation to participate in school-enterprise cooperation.