Evidence that open educational resources (OER) can decrease college students' educational cost without harm to their course performance on different subjects has been well documented, but student motivation to use OER for learning is underexplored. This study investigated college students' achievement goals of using OER from the perspective of expectancy-value theory. We recorded the survey responses of 246 college students in an education course at a public university in the southeast of the United States of America for analysis. We established a structural equation model to investigate the relationship between their task value beliefs in using OER and their course achievement goals. The findings show that the students' perceived usefulness of OER positively predicted their mastery-approach goals but negatively predicted their performance-approach goals. In addition, their self-estimated cost of learning with OER predicted their mastery-avoidance goals. We discuss practical implications for facilitating college students' motivation toward using OER.