E-commerce emerges from the integration of internet technology and business models, shaped by technological advancements, market demand shifts, and policy changes, leading to distinct industry characteristics across eras. Upper Echelons Theory posits that entrepreneurs’ backgrounds and traits influence corporate performance in complex, multifaceted ways, necessitating non-linear research approaches. This paper employs the fs QCA method to explore the configuration characteristics of e-commerce entrepreneurs across different temporal contexts and their impact on performance. Analyzing 89 cross-sectional cases from 1996 to 2023, the study identifies diverse high-performance paths for entrepreneurs in different eras. Key findings include: First, high-performance paths exhibit significant diversity and era-specific characteristics. Second, risk propensity, business acumen, and technical background are core conditions for achieving high performance. Third, the policy environment and technological changes significantly shape entrepreneurial configurations. This study enriches individual-level research on entrepreneurs and offers insights for e-commerce companies in establishing and selecting leaders.