This review presents the computational method of topic modeling to identify core topics and time trends in research on X-ray fluorescence (XRF) and its application to cultural heritage. Topic modeling is an approach to text mining based on unsupervised machine learning, which helps to determine core topics within a vast body of text. Due to the large amount of published work on X-ray fluorescence in the area of cultural heritage, traditional literature review has become impractical, inefficient, time-consuming, and potentially less reliable. Therefore, it is important to take stock of which topics have been core to such research and whether specific time trends can be identified within them. Using topic modeling, this review aims to reveal core topics and trends in research on XRF analysis of painted heritage objects by examining 982 articles collected from Web of Science. Within this dataset of articles, ten topics have been identified. The identified topics can be clustered in three main categories: the methods used, the objects studied, and the specific materials studied. In terms of trends in topic share since 2010, it is especially noteworthy to see that the share of articles focused on the identification and study of painting materials and techniques has more than doubled. Similarly, another impressive increase can be observed for articles centered on advanced imaging spectroscopic techniques, such as macro X-ray fluorescence (MA-XRF) and reflectance hyperspectral imaging, for the study of easel paintings. The share of attention within XRF literature given to imaging spectroscopic techniques tripled between 2010 and 2017, though stabilizing in the subsequent years. Conversely, the share of articles which specifically deal with the development and improvement of energy dispersive X-ray fluorescence (ED-XRF) spectroscopic techniques (i.e., portable ED-XRF, confocal micro-XRF, micro-grazing exit XRF) for the elemental analysis (including elemental depth profiling) of painted heritage objects has declined sharply.