Nursing homes are one type of long-term care organizations. Volunteers may be unwilling to serve regularly in nursing homes affiliated with hospitals. In this study, we used the planned behavior theory to investigate the intention of hospital volunteers to regularly serve in nursing homes. We performed a purposive sampling of volunteers in the nursing homes affiliated with six hospitals in Taiwan. The total number of questionnaires delivered was 600, and 447 valid questionnaires with an effective response rate of 74.5%. According to the results from a structured equation model, the hospital volunteer’s attitude (e.g., learning techniques, foreknowledge, learning services, and perceptions regarding life and care), subjective norm (e.g., number of nursing homes, family and friends, and other volunteers), and the perceived behavioral control (e.g., skill shortage, sense of accomplishment, and treatment mood), all revealed a positive intention (e.g., easiness, willingness, and possibility). The results conformed to the theoretical framework of planned behavior theory. Moreover, among the three dimensions influencing behavior intention, the subjective norm played the most important role thereby indicating the importance of significant others. Our study suggested that nursing homes would be able to recruit volunteers, not only through the office of social workers, but also by asking for help from the hospital’s volunteers. Furthermore, nursing homes could hold orientation seminars to describe the contents of their services to the volunteers when they participated in the on-the-job training programs held by the office of the social workers. Such activities may enhance the beliefs of the volunteers, and by doing so, increase their behavior intentions to provide regular services in the nursing homes.