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The photoinduced relaxation dynamics of nucleobases and their thionated analogs have been investigated extensively over the past decades motivated by their crucial role in organisms and their application in medical and biochemical research and treatment. Most of these studies focused on the spectroscopy of valence electrons and fragmentation. The advent of ultrashort x‐ray laser sources such as free‐electron lasers, however, opens new opportunities for studying the ultrafast molecular relaxation dynamics utilizing the site‐ and element‐selectivity of x‐rays. In this review, we want to summarize ultrafast experiments on thymine and 2‐thiouracil performed at free‐electron lasers. We performed time‐resolved x‐ray absorption spectroscopy at the oxygen K‐edge after UV excitation of thymine. In addition, we investigated the excited state dynamics of 2‐tUra via x‐ray photoelectron spectroscopy at sulfur. For these methods, we show a strong sensitivity to the electronic state or charge distribution, respectively. We also performed time‐resolved Auger–Meitner spectroscopy, which shows spectral shifts associated with internuclear distances close to the probed site. We discuss the complementary aspects of time‐resolved x‐ray spectroscopy techniques compared to optical and UV spectroscopy for the investigation of ultrafast relaxation processes. [ABSTRACT FROM AUTHOR]