The information of metal constituents in complex samples is crucial for understanding the physicochemical properties and formation mechanisms of samples. Moreover, direct analysis of metal constituents in such samples without sample pretreatment not only enhances analytical efficiency but also facilitates the elucidation of physical and chemical relationships among the components, which has attracted wide spread attention. Mass spectrometry possesses remarkable advantages in both qualitative and quantitative analyses of metal constituents. This review systematically summarizes recent advances in mass spectrometry-based methods for the direct analysis of metal constituents over the past decade. Unlike existing reviews, this work offers a overview of both hard ionization and soft ionization mass spectrometry techniques applied to the direct analysis of metallic elements. In this review, we present the fundamental principles of mass spectrometry relevant to this application, highlight representative applications across diverse fields such as environmental science, geology, and materials science, and critically discuss the advantages and limitations of each approach. Finally, we outline future research directions for advancing mass spectrometry in the direct analysis of metal constituents. This review provides valuable insights for the development of high-performance analytical methods for metal constituent analysis.