Associative processes play a major role in research on human thinking, especially creativity. One of the most influential models emphasizing associative processes in creative thinking was introduced by Mednick (Psychological Review, 69, 220–232, 1962), who developed the remote associates test (RAT) as a domain-general measure of individual differences in associative hierarchies. Although S. Mednick’s theoretical framework has recently regained much attention, the fundamental psychometric assumptions and underlying cognitive processes involved in the RAT remain controversial. We carried out two studies to evaluate these issues. In the first, a confirmatory factor analysis showed that a single latent factor accounted for the ability to solve RAT problems, despite their psycholinguistic heterogeneity. Subsequent regression analyses indicated that cue–solution associative remoteness substantially determined the difficulty of RAT problems, accounting for about 80% of variance. In the second study we used a newly developed associative chain test (ACT), which assesses lexical–semantic and executive measures during associative processing. We found that performance on the RAT was related to lexical–semantic (higher response remoteness and lower response commonness) but not to executive (response inhibition and switching) ACT measures. Overall, our findings indicate that the RAT reflects a coherent ability to access and combine remote elements in lexical–semantic and associative networks without considerably engaging executive attention. Although the validity and utility of the RAT was supported, we propose that the ACT provides a more complex and fine-grained tool for the assessment of associative processing.