The reactions of py‐hz ligands (L1–L5) with Pb(CF3SO3)2⋅H2O resulted in some rare examples of discrete single‐stranded helical PbII complexes. L1 and L2 formed non‐helical mononuclear complexes [PbL1(CF3SO3)2]⋅CHCl3 and PbL2(CF3SO3)2][PbL2CF3SO3]CF3SO3⋅CH3CN, which reflected the high coordination number and effective saturation of PbII by the ligands. The reaction of L3 with PbII resulted in a dinuclear meso‐helicate [Pb2L3(CF3SO3)2Br]CF3SO3⋅CH3CN with a stereochemically‐active lone pair on PbII. L4 directed single‐stranded helicates with PbII, including [Pb2L4(CF3SO3)3]CF3SO3⋅CH3CN and [Pb2L4CF3SO3(CH3OH)2](CF3SO3)3⋅2 CH3OH⋅2 H2O. The acryloyl‐modified py‐hz ligand L5 formed helical and non‐helical complexes with PbII, including a trinuclear PbII complex [Pb3L5(CF3SO3)5]CF3SO3⋅3CH3CN⋅Et2O. The high denticity of the long‐stranded py‐hz ligands L4 and L5 was essential to the formation of single‐stranded helicates with PbII.