We report the synthesis of [(L)DyIII(Cy3PO)2]·[BPh4] (1-Dy) (where H2L = 2,6-diacetylpyridine bis-benzoylhydrazone and Cy = cyclohexyl) which crystallized in the triclinic, P1̄ space group. The local geometry around Dy(iii) in 1-Dy was found to be pentagonal bipyramidal (pseudo-D5h). The AC magnetic susceptibility measurements performed on 1-Dy and on its diluted 1-Y(Dy) samples showed a typical single-molecule magnet signature revealed by the appearance of AC-frequency dependent out-of-phase susceptibility signals in the absence of a static magnetic field. The out-of-phase AC susceptibility signals were well resolved on the application of a small magnetic field (HDC = 500 Oe) and yielded an energy barrier for magnetization flipping of Ueff/kB = 50 K for the diluted derivative. The magnetic studies on 1-Dy and 1-Y(Dy) and data analysis further confirm that Raman and QTM under-barrier magnetic relaxations play a crucial role in lowering Ueff despite the almost axial nature of the Dy(iii) ion in 1-Dy. We have rationalized these observations through detailed ab initio calculations performed on the X-ray crystal structure of 1-Dy. © 2023 The Royal Society of Chemistry.