Being religious or having spiritual beliefs has been linked to improved health and well-being in several empirical studies. Potential underlying mechanisms can be suggested by psychometrically reliable and valid indices. Two self-report measures of religiosity/spirituality were completed by a cohort of older adults: the Religious Involvement Inventory and the Spiritual Well-being Scale. Both were analyzed using principal components analysis and the Mokken scaling procedure. The latter technique examines whether items can be described as having a hierarchical structure. The results across techniques were comparable and hierarchical structures were discovered in the scales. Analysis of the hierarchy in the RII items suggested the latent trait assesses the extent to which an individual's belief in God influences their life. Examining scales with a range of psychometric techniques may give a better indication of the latent construct being assessed, particularly the hierarchies within these which may be of interest to those investigating religiosity-health associations.