The rapid growth in demand for ‘critical’ metals, including Pd, may raise a potential obstacle to the widespread adoption of low-carbon energy technologies. The development of more efficient and sustainable processing technologies is essential for the exploitation of the deposits and managing the mining tailings. Kotulskite PdTe, a common mineral in natural ores, dissolves up to 40.3 at% of Bi. Due to their small size, kotulskites are challenging to characterize by conventional methods, making synthetic phases a key alternative for detailed investigations. Although bismuthian kotulskites have been extensively studied, the state of Pd remains unclear due to the lack of spectroscopic studies, leaving key questions on the Pd local atomic environment and variations of Pd-Te/Bi interatomic distances unanswered. Hence, we propose investigating the synthetic bismuthian kotulskite solid solution series and natural kotulskites at the Pd K-edge using XAS at different temperatures.