This study identified predictors of satisfaction with care services among family members of older adults residing in long-term care facilities (LTCFs). In this cross-sectional descriptive study, the participants were 330 family members of older adult residents of LTCFs in Seoul, Gyeonggi, Gangwon, Gyeongbuk, and Chungnam, Korea. Data were collected from July to October 2018 using a structured self-report questionnaire. Data were analyzed using descriptive statistics, independent t-testing, one-way ANOVA, Kruskal–Wallis testing, Pearson’s correlation coefficients, and hierarchical multiple regressions. The most important predictors of satisfaction with care services were satisfaction with the physical housing environment (β = 0.49, p < 0.001), caregiving stress (β = −0.30, p < 0.001), the facility’s size (β = −0.13, p = 0.001), the number of visits to the facility (β = −0.10, p = 0.024), and the number of family members who participated in the decision to place the relative in a facility (β = 0.09, p = 0.033). This study is significant because it provides fundamental data for qualitatively improving care services in LTCFs. Based on the results, strategies should be developed to relieve caregiving stress among family members and improve satisfaction with the physical housing environment.