The hydration and pore structure of hardened cement pastes containing various amounts of alkali and hexylene glycol -a shrinkage-reducing admixture (SRA)- are studied. Until three months, SRA retards cement paste hydration regardless of alkali content; after seven days at most, this retardation diminishes with time. Alkalis increase the hydration degree at early ages for all pastes. The pore structure coarsens with the SRA: both the specific surface area and the volume of pores with a 5 nm entry size decrease in the presence of the SRA. The magnitude by which the SRA impacts the pore structure reduces with alkali. In alkali media, the C-S-H gel uptakes alkalis and aluminum; modifying the C-S-H structure, the gel pore volume, and the interlayer space. The SRA depletes the alkalis from the solution and may increase the C-S-H alkali uptake, which could lead to changes in the gel pore volume and specific surface area.