This study highlighted how particular intersections of personal characteristics were related to Motivation to Learn (MtL) among adults. MtL is a prerequisite for adult education and training participation. However, little is known about MtL across subpopulations due to several methodological limitations. This study developed a national profile of MtL by key subpopulations that are defined by combinations of age, gender, education level, and literacy proficiency in the United States. Data were obtained from 2012/2014/2017 Program for International Assessment of Adult Competencies (PIAAC) restricted use file (N = 8400). The alignment optimization (AO) method was employed to estimate subpopulation means of a PIAAC-based latent MtL construct. Subpopulations with younger age, greater educational attainment, and higher literacy proficiency showed significantly greater MtL.