Single-molecule magnets (SMMs) based on dysprosocenium cations, [Dy(CpR)2]+ (CpR = substituted cyclopentadienyl), have set record effective energy barriers to magnetic reversal (Ueff) and temperatures at which open magnetic hysteresis is observed (TH), due to their highly axial crystal fields (CFs) and rigid ligand frameworks. Dysprosium bis(amide) cations, [Dy(NR2)]+ (R = bulky silyl, aryl), can potentially show superior SMM properties as more charge-dense N-donor atoms can enforce stronger axial CFs to increase Ueff, but these more flexible ligands can also promote under-barrier magnetic relaxation processes that diminish TH. Here we combine the favorable SMM properties of each ligand in a single complex, [Dy{N(SiiPr3)2}(Cp*)][Al{OC(CF3)3}4] (1-Dy; Cp* = C5Me5). We find that 1-Dy has large magnetic anisotropy, with Ueff = 2191(33) K; this is comparable with the best-performing dysprosium CpR-based SMMs, but lower than the dysprosium bis(amide)-alkene complex [Dy{N(SiiPr3)[Si(iPr)2C(CH3)=CHCH3]}{N(SiiPr3)(SiiPr2Et)}][Al{OC(CF3)3}4] (Ueff = 2652(16) K). A combination of the bent N–Dy–Cp*cent angle (ca. 152.5(2)°) and flexible amide substituents of 1-Dy limits TH to 73 K, which is below the record TH value of 100 K for the bis(amide)-alkene. Together, this work shows that dysprosium SMMs containing one π-aromatic and one monodentate ligand can have comparable Ueff values to bis-π-aromatic complexes, but in common with dysprosium bis(amide) complexes they show a greater sensitivity of inter-ligand angle towards under-barrier relaxation processes. This new class of dysprosium complexes are promising candidates for high-temperature SMMs, and it is likely that large improvements on this first example can be made with exquisite control of molecular geometry.