The development of an elution-free solid-phase extraction (SPE) process is of special interest in sample pretreatment. Due to the phase-change merits at relatively low temperatures and easy dissolution in n-hexane, wax spheres show great potential in this field. However, the conventional wax spheres possess a low affinity towards the target analytes when they are used as SPE adsorbents. In this study, using octadecanoic acid as the functional monomer and wax as the matrix, molecularly imprinted wax (MIW) spheres were successfully prepared. The obtained MIW spheres displayed remarkable molecular recognition ability and high selectivity towards the template. Interestingly, the as-synthesized molecularly imprinted wax (MIW) could be dissolved in n-hexane or melted by heating for subsequent fluorescence and mass spectrum analysis without the target elution process. Moreover, the melted MIW exhibited high repeatability, sensitivity and specificity for solid-state fluorescence detection. We believe that the imprinting method presented in this study will open a new window in analytical chemistry.