This paper reports a new method for the synthesis of α,ω-primary-dihydroxy PIBs (HO–PIB–OH) with a fully aliphatic backbone. Three aliphatic difunctional initiators with tertiary-methoxy, tertiary-chloride and tertiary-hydroxyl end groups (TMHDiOMe, TMHDiCl and TMHDiOH) were screened in conjunction with TiCl₄ and DMA in a solution system (hexane–CH₃Cl, 60/40, v/v). TMHDiOMe yielded only traces of PIB, while TMHDiOH and TMHDiCl yielded PIBs with a mixture of end group structures. The same initiators were also screened in heterogeneous systems (CH₃Cl or CH₂Cl₂). TMHDiOMe/TiCl₄ yielded no polymer in either diluent, CH₃Cl, and TMHDiOH/TiCl₄ led to olefinic end groups. While TMHDiCl/TiCl₄ resulted in clean Cl–PIB–Cl in CH₃Cl, the I_eff values were low and TMHDiCl was very unstable and difficult to isolate. Premixing TMHDiOH with TiCl₄ in CH₃Cl led to the in situ formation of TMHDiCl. Addition of hexane and IB, followed by end-capping with allyltrimethylsilane resulted in the formation of allyl–PIB–allyl. Click chemistry with HS–CH₂–CH₂–OH yielded α,ω-primary-dihydroxy-PIB (HO–PIB-OH) with M_n = 4085 g mol⁻¹ and Đ_M = 1.2. ¹H-NMR analysis verified the structure of the HO–PIB–OH.