Over the past decade, single-molecule fluorescence studies have elucidated the structure-function relationship of numerous nucleic acids enzymes. In particular, the real-time observation of individual ribozymes has unveiled the dynamic behavior of complex RNA systems in unprecedented detail, revealing the presence of transient intermediate states and their kinetic pathways. Here, we will provide an overview of how single-molecule fluorescence can been used to explore the dynamics of RNA folding and catalysis by present examples from the smallest motifs (e.g., kissing hairpins) to some of the largest ribozymes (such as group II introns and the spliceosome).