<p>Quasi-one-dimensional RbMn₆Bi₅, the first pressure-induced ternary Mn-based superconductor, exhibits a phase diagram analogous to those of cuprate and iron-based superconductors, with superconductivity neighboring antiferromagnetic order. Here, we use ⁵⁵Mn and ⁸⁷Rb nuclear magnetic resonance (NMR) to unravel its magnetic structure and fluctuations. Above the Néel temperature (<i>T</i>_N), strong antiferromagnetic fluctuations dominate, characteristic of a paramagnetic state with pronounced spin-lattice relaxation rate enhancement. Below <i>T</i>_N, a first-order phase transition establishes a commensurate antiferromagnetic order, where Mn atoms at the pentagon corners exhibit distinct magnetic moments with different orientations, while the central Mn atom carries no magnetic moment. The complex magnetic architecture, revealed by zero-field and high-magnetic-field NMR spectra, contrasts with earlier neutron diffraction models proposing uniform spin density waves, instead supporting localized moment ordering with charge rearrangement. The proximity of robust antiferromagnetic fluctuations to the high-pressure superconducting phase suggests a potential role for magnetic excitations in mediating unconventional Cooper pairing, akin to paradigmatic high-<i>T</i>_<i>c</i> systems. These findings provide critical insights into the interplay between geometric frustration, magnetic order, and superconductivity in manganese-based materials.</p>