Confidence levels of students enrolled in open access programs and undergraduate courses were measured at the University of Newcastle. The open access science students aimed to gain access to undergraduate studies in various disciplines at University. The undergraduate students were enrolled in a variety of degrees and were surveyed during their first semester of study in chemistry. The "third person effect" was used to measure the confidence levels of these two groups of students. Using this technique, the study examined the extent to which students undertaking open access programs and undergraduate course were confident in learning. It was found that a lack of confidence arises predominantly in females who were also less optimistic in predicting the performance of a third person beginning their respective course. The results from open access students collected from consecutive years were compared to the results of undergraduate chemistry students. The findings were significant in that the students in the first year of undergraduate chemistry had significantly lower confidence than students in open access courses who are traditionally thought of disadvantaged in some way. The paper argues the need to build confidence in students who experience high levels of uncertainty in learning. Building confidence in all students in early stages is known to optimise academic outcomes.