Open-vocabulary semantic segmentation aims at segmenting arbitrary categories expressed in textual form. Previous works have trained over large amounts of image-caption pairs to enforce pixel-level multimodal alignments. However, captions provide global information about the semantics of a given image but lack direct localization of individual concepts. Further, training on large-scale datasets inevitably brings significant computational costs. In this paper we propose FreeDA, a training-free diffusion-augmented method for open-vocabulary semantic segmentation, which leverages the ability of diffusion models to visually localize generated concepts and local-global similarities to match class-agnostic regions with semantic classes. Our approach involves an offline stage in which textual-visual reference embeddings are collected, starting from a large set of captions and leveraging visual and semantic contexts. At test time, these are queried to support the visual matching process, which is carried out by jointly considering class-agnostic regions and global semantic similarities. Extensive analyses demonstrate that FreeDA achieves state-of-the-art performance on five datasets, surpassing previous methods by more than 7.0 average points in terms of mIoU and without requiring any training. Our source code and models will be made publicly available.