Molecularly imprinted polymers (MIPs) are well historically known class of material that have wide range of applications. Regarding chemical analysis, MIPs could replace biogenic materials, such as antibodies, to impart the required selectivity for analytical method. Apart from other purposes, preparing a MIP for analysis requires particular attention to certain aspects critically affecting the overall efficiency of the imprinting process. In this review we emphasized the critical steps during MIP preparation and characterization that would significantly affect the assessment of imprinting efficiency. MIP preparation starts with the selection of suitable monomers based on the nature of the used template. The template tends to form a stable complex with the used monomers. According to the type of bond formed between template and monomer molecules, three imprinting approaches are reported: covalent, non-covalent, and semi covalent. Then, polymerization of that complex takes place to produce MIP with template occupied binding sites or imprint cavities. So, for the completion of imprinting process and hence vacant cavity production, a suitable effective extraction technique is used. The assessment of template extraction process can be either direct, by template detection in the washing solution, or indirect, by measuring certain physical property of the polymer before and after template removal. Finally, the different parameters determined to assess the imprinting efficiency were summarized and the different sources of errors were addressed.