Leveraging the supportive role of venture capital-style spin-off entrepreneurship in large enterprises to foster and expand emerging and future industries is a key requirement for building a modern industrial system. This paper constructs an evaluation index system for the implementation pathways of venture capital-style spin-off entrepreneurship in large enterprises and further explores the suitable scenarios for different implementation pathways. The study finds that the endowments of entrepreneurial teams, the strengths of large enterprises, and external environmental factors constitute the evaluation index system for the implementation pathways of venture capital-style spin-off entrepreneurship in large enterprises; the abrupt pathway is the optimal implementation pathway for achieving venture capital-style spin-off entrepreneurship in large enterprises. Further analysis reveals that the abrupt path demonstrates significant advantages in core indicators such as team goal alignment and internal corporate synergy, making it suitable for enterprises with abundant resources and high risk tolerance; the gradual path stands out for its robustness and, leveraging industrial ecosystem advantages, is suitable for resource-constrained and risk-averse enterprises; the iterative path is balanced across all dimensions and aligns with scenarios where both resources and risk levels are moderate; the hybrid path has low suitability due to insufficient team innovation and internal synergy. This paper not only reveals the implementation pathways and suitable scenarios for venture-capital-style spin-off entrepreneurship in large enterprises but also provides empirical evidence to support the nation’s efforts to refine its innovation-driven development strategy and build a modern industrial system through patient capital.