Soluble macromolecules are essential to Nature's control over biomineral formation. Following early studies where macromolecules rich in aspartic and glutamic acid were extracted from nacre, research has focused on the use of negatively charged additives to control calcium carbonate precipitation. It is demonstrated that the positively charged additive poly(allylamine hydrochloride) (PAH) can also cause dramatic changes in calcite morphologies, yielding thin films and fibers of CaCO3 analogous to those produced with poly(aspartic acid) via a so-called PILP (polymer-induced liquid precursor) phase. The mechanism by which PAH induces these effects is investigated using a range of techniques including cryo transmission electron microscopy (TEM), Raman microscopy, and thermogravimetric analysis, and the data show that hydrated Ca2+/PAH/CO32- droplets initially form in solution, before coalescing and ultimately crystallizing to give calcite, together with small quantities of vaterite. It is suggested that it is the initial formation of hydrated Ca2+/PAH/CO32- droplets that is key to this process, rather than a specific polymer/mineral interaction. These results are discussed in terms of their relevance to biomineralization processes and highlight the opportunity for using counter-ion-induced phase separation of polyelectrolytes as a method for generating minerals with non-crystallographic morphologies.