Although the social exchange relationships between employers and employees are increasingly important to the performance of safety management systems, the psychological effects of work attitudes on this relationship have been less studied. Using a sample of first-line operators and their supervisors from 188 facilities in Taiwan which had Occupational Health and Safety Assessment Series 18000 (OHSAS 18000) certification, the current research conducted an empirical investigation of the influence of safety climate on organizational citizenship behavior (OCB). Work attitude was used to disclose the psychological effect. Research results indicated that (a) safety climate was a significant predicator of OCB, (b) the psychological effect significantly influenced social exchange relationships, and (c) job satisfaction showed a stronger mediating influence than organizational commitment due to the frequent top management turnover. Discussions and implications are also addressed.