The design of a virtual reality (VR) cultural application is aimed at supporting the steps of the learning process-like concrete experimentation, reflection and abstraction—which are generally difficult to induce when looking at ruins and artifacts that bring back to the past. With the use of virtual technologies (e.g., holographic surfaces, head-mounted displays, motion—cation sensors) those steps are surely supported thanks to the immersiveness and natural interaction granted by such devices. VR can indeed help to symbolically recreate the context of life of cultural objects, presenting them in their original place of belonging, while they were used for example, increasing awareness and understanding of history. The ArkaeVision VR application takes advantages of storytelling and user experience design to tell the story of artifacts and sites of an important cultural heritage site of Italy, Paestum, creating a dramaturgy around them and relying upon historical and artistic content revised by experts. Visitors will virtually travel into the temple dedicated to Hera II of Paestum, in the first half of the fifth century BC, wearing an immersive viewer–HTC Vive; here, they will interact with the priestess Ariadne, a digital actor, who will guide them on a virtual tour presenting the beliefs, the values and habits of an ancient population of the Magna Graecia city. In the immersive VR application, the memory is indeed influenced by the visitors’ ability to proceed with the exploratory activity. Two evaluation sessions were planned and conducted to understand the effectiveness of the immersive experience, usability of the virtual device and the learnability of the digital storytelling. Results revealed that certainly the realism of the virtual reconstructions, the atmosphere and the “sense of the past” that pervades the whole VR cultural experience, characterize the positive feedback of visitors, their emotional engagement and their interest to proceed with the exploration.