Virtual tourism is a key emerging form of digital sustainable tourism that supports the sustainable transformation of the tourism industry. Although scholars have increasingly investigated how virtual tourism experiences influence on-site destination visit intentions, there is still a lack of systematic explanations for the underlying formation mechanism. Furthermore, research on the experience-behavior transformation mechanism of virtual tourism platforms remains inadequate. To fill these gaps, this study integrates the Stimulus-Organism-Response (SOR) framework, Technology Readiness Model (TR) and Technology Acceptance Model (TAM) to construct an emotional-technology psychology–cognition–behavior chain-mediated model. Using 683 valid questionnaires, the proposed model was examined via structural equation modeling and Bootstrap analysis. Results reveal that perceived enjoyment strengthens technology optimism and alleviates technology insecurity. Technology optimism positively predicts perceived usefulness and ease of use, while technology insecurity shows a negative effect on perceived usefulness. Perceived ease of use enhances perceived usefulness, which further promotes intention to use the platform’s virtual modules, thereby increasing real destination visit intentions. Perceived ease of use enhances intention to use the platform’s virtual modules, while increasing real destination visit intentions. Perceived ease of use enhances intention to use the platform’s virtual modules, and further promotes real destination visit intentions through chain-mediated pathways. Notably, perceived enjoyment exerts significant chain-mediating effects through three pathways: technology optimism → perceived usefulness → virtual module usage intention; technology optimism → perceived ease of use → virtual module usage intention; and technology optimism → perceived ease of use → perceived usefulness → virtual module usage intention. This study extends the application of the SOR framework to digital sustainable tourism contexts, clarifies micro-psychological transformation mechanisms, and provides practical implications for platform optimization, destination marketing and tourism development.