When people interact with their environment, they acquire an understanding of its probabilistic structure through experiences. The premise of the decisions from experience paradigm (Hertwig & Erev, 2009) is that people base their decisions on their experiences. In this study, we offer a psychoeconomic and psychocognitive account for decisions from experience and propose answers to the questions on how one’s probabilistic environment and sample size influence decision-making and how learning is reflected in autonomous sampling behavior. We presented N = 60 participants with an adaptation of the sampling protocol and conducted choice and reaction time (RT) analyses including a drift diffusion modulation (DDM). Regarding the psychoeconomic choice analysis, the ambiguity of one’s environment holds a greater influence on the accuracy of one’s decision-making than the quantity of one’s experiences. Furthermore, with cumulating experiences, people’s proximal perception converges with their distal environment and people tend to base their choices on their experiences. Regarding the psychocognitive RTs analysis, we observe a decline of RTs throughout a sampling phase and qualitative differences between a decision to continue sampling and the decision to stop sampling. These can be explained by variations in cognitive parameters of the DDM between the beginning and end of a sampling phase. People seem to exhibit a general bias toward exploring their environment and maintaining their autonomy, a decrease in the amount of evidence to be accumulated, and differences in evidence accumulation itself. Investigating learning in autonomous sampling behavior through DDMs seems to be a promising path for future research.