The study of quantum spin systems is at the forefront of condensed matter research due to the fascinating behaviour they can display. An interesting source for quantum S = 1/2 moments in magnetic materials is the 3d1 Ti3+ ion. The magnetic response of Ti3+-based materials strongly depends on various competing energy scales of crystal field states, spin-orbit coupling and magnetic exchange. Often, this competition can give rise to exotic magnetic ground states. Here, we propose to perform a high-resolution structural study of two polymorphs of KTi(C2O4)2·2H2O, which contain two different magnetic sublattices of Ti3+ S = 1/2 moments, each with different point symmetries at the Ti3+ ion sites. The determined structures will form a crucial foundation for our understanding of the crystal fields in each of the phases, and hence the origin of their markedly different magnetic behaviour.