Entrepreneurial spiritual capital is the high-level spiritual capital of entrepreneurs in their core values, outlook on life, world outlook and other ultimate beliefs. It can lead entrepreneurs to combine and use the various elements of the organization. It is of great significance to the growth of employees and the sustainable development of enterprises. In an organizational environment, spiritual entrepreneurs influence employees’ psychological capital level and psychological security perception by building great organizational vision and firm beliefs, and giving altruistic love to employees to meet their spiritual needs of pursuing excellence, self-realization and being recognized by others, to further influence employees’ initiative and proactive behavior. Meanwhile, due to individual differences in the understanding of information in the organizational environment, when employees have different perceptions of the proximity of the relationship with entrepreneurs, their psychological capital level and perception of psychological security will be affected. So based on the survey of 294 employees in 15 high-tech enterprises such as Unicorn, this paper explores the relationship between entrepreneurs’ spiritual capital and employees’ work initiative according to the social information processing theory. The results show that: spiritual capital has a positive impact on employees’ proactive behavior; psychological capital and psychological safety have a significant mediating effect; under the relational closeness moderating, which means the subjective experience of employees’ emotional affinity and psychological stickiness of entrepreneurs, entrepreneurial spiritual capital has a positive impact on employees’ initiative and proactive behavior through the mediating role of psychological sense of security. 　　Although there are many problems in this study which need to be further explored, we still find that entrepreneurs’ spiritual capital has important value in the growth of employees and the future development of enterprises. We propose the impact of entrepreneurial spiritual capital on employees’ proactive behavior in order to encourage future managers to focus on self-management and employees’ development, learn to respect human nature, pay more attention to creating the spiritual organizational climate. Just like many scholars said, the improvement of their spiritual pursuit, the cultivation of learning ability, and the pursuit of a high degree of soul will not only affect every individual of enterprises, but also greatly promote the realization of organizational goals and values.