A primary cause of occupational accidents is on-site workers not having proper or even adequate safety knowledge and awareness, leading to them failing to employ safety measures, equipment, or behavior to protect themselves. The complexity of construction projects and changes in organizational personnel complicate the safety knowledge transfer process. Therefore, to reduce occupational accidents in the construction industry, this study explored the on-site safety knowledge transfer process as well as its relationship with a safe working environment; it did this to understand the associations between various constructs in the process, which could be used as a reference for management personnel to promote on-site safety education and behaviors. This would allow safety knowledge to be learned and practiced by on-site workers, changing their unsafe behaviors and creating a safe on-site work environment. This study used structural equation modeling to empirically study the relationship between various constructs during safety knowledge transfer on a construction site. The results revealed that an excellent safety knowledge transfer environment can lead to favorable safety behavior as well as safety knowledge application and inspiration of on-site workers, which would affect their safety behaviors. More satisfactory safety behaviors of on-site workers could produce a safer working environment on the construction site. Moreover, although safety application and inspiration do not directly affect the safety of a work environment, they do so indirectly through safety behaviors.