With the development of communication technology and the COVID-19 pandemic, it has become increasingly common for employees to maintain work connectivity after-hours, which has a significant impact on their psychological state at work. However, most of the existing studies have not reached a consensus on the impact of work connectivity behavior after-hours on employees’ psychological state at work, and the existing studies have led to theoretical and practical disagreements. Based on the Job Demands–Resources model, we built a two-path model of work autonomy and emotional exhaustion to explore the impact of work connectivity behavior after-hours on work engagement. In addition, we compared the differences between different workplace statuses (managers and ordinary employees). Through surveys and analyses of 257 employees, the results show that work connectivity behavior after-hours positively impacts employees’ work engagement by increasing managers’ work autonomy and reducing ordinary employees’ emotional exhaustion. This study not only reveals that work connectivity behavior after-hours positively affects work engagement but also illustrates the differences in impact between managers and ordinary employees; these findings contribute to the development of a consensus on the influence of work connectivity behavior after-hours on employees’ psychological state at work, which provides insights for organizations seeking to manage work connectivity behavior after-hours, for example, by adopting different connectivity management strategies for employees with different workplace statuses.