Molecularly imprinted polymers (MIP) have shown their potential as artificial and selective receptors for environmental monitoring. These materials can be tailor-made to achieve a specific binding event with a template through a chosen mechanism. They are capable of emulating the recognition capacity of biological receptors with superior stability and versatility of integration in sensing platforms. Commonly, these polymers are produced by traditional free radical bulk polymerization (FRP) which may not be the most suitable for enhancing the intended properties due to the poor imprinting performance. To improve the imprinting technique and the polymer capabilities, controlled/living radical polymerization (CRP) has been used to overcome the main drawbacks of FRP. Combining CRP techniques such as RAFT (reversible addition–fragmentation chain transfer) with MIP has achieved higher selectivity, sensitivity, and sorption capacity of these polymers when implemented as the transductor element in sensors. The present work focuses on RAFT-MIP design and synthesis strategies to enhance the binding affinities and their implementation in environmental contaminant sensing applications.