Abstract In this paper, we demonstrate computationally the existence of magnetoelectric multipoles, arising from the second-order term in the multipole expansion of a magnetization density in a magnetic field, in non-centrosymmetric magnetic metals. While magnetoelectric multipoles have long been discussed in the context of the magnetoelectric effect in non-centrosymmetric magnetic insulators, they have not previously been identified in metallic systems, in which the mobile carriers screen any electrical polarization. Using first-principles density functional calculations, we explore three specific systems: first, a conventional centrosymmetric magnetic metal, Fe, in which we break inversion symmetry by introducing a surface, which both generates magnetoelectric monopoles and allows a perpendicular magnetoelectric response. Next, the hypothetical cation-ordered perovskite, SrCaRu2O6, in which we study the interplay between the magnitude of the polar symmetry breaking and that of the magnetic dipoles and multipoles, finding that both scale proportionally to the structural distortion. Finally, we identify a hidden antiferromultipolar order in the non-centrosymmetric, antiferromagnetic metal Ca3Ru2O7, and show that, while its competing magnetic phases have similar magnetic dipolar structures, their magnetoelectric multipolar structures are distinctly different, reflecting the strong differences in transport properties. This article is part of the theme issue ‘Celebrating 125 years of Oliver Heaviside's ‘Electromagnetic Theory’’.