The objective of this thesis was to explore novel approaches for controlling morphologies and molecular recognition behaviour of polymers and to use these strategies in conjunction with the molecular imprinting technique in order to either enhance polymer performance in quartz crystal microbalance (QCM) sensor applications, or as an alternative to conventional solvents of polymerization. In Papers I and II, the use of liquid crystalline media in the synthesis of molecularly imprinted polymers was demonstrated. When used in conjunction with the molecular imprinting technique the LC media induced hierarchical material architectures, which provided an enhancement of QCM-sensor sensitivity. The use of a class of novel solvents, so-called “non-ionic deep eutectic solvents (ni-DESs)”, was explored in polymer synthesis, Paper III, and for molecularly imprinted polymer synthesis, Paper IV. The use of these solvents produced polymers with morphological features comparable to those prepared in conventional solvents, and sensitivities towards bupivacaine template were observed. Collectively these results present a new strategy for generating new hierarchical polymer architectures and a new class of solvent for polymer synthesis, which can also be used for molecular imprinting, that can be used as an alternative to conventional and sometimes flammable or toxic polymerization solvents.