The Interview Schedule for Social Interaction (ISSI) is a measurement widely used to evaluate social support. Based on the two dimensions (the availability of attachment and the availability of social integration) of ISSI, the Structural-Functional Social Support Scale (SFSSS) is used to assess the availability of social support, which consists of structural and functional social support dimensions. However, the factor structure, reliability, and validity of this scale have not been tested. This study examined the psychometric properties of SFSSS in a sample of 1,631 Chinese older adults. In Study 1 (n = 306), the SFSSS was found to demonstrate an adequate fit to a two-factor structure; this structure was replicated in Study 2 (n = 1,325). The measure was found to have an adequate internal consistency, acceptable composite reliability, and reasonably high four-week test-retest reliability. It also showed good convergent, discriminant, and concurrent validity. The measurement invariant across gender was supported. Overall, the SFSSS was a valuable tool for assessing the structural and functional aspects of social support among older adults in China.