Oxazepam, one of the most frequently prescribed anxiolytic drugs, is not completely removed from waste waters with conventional treatment processes. It can thus also be found in environmental waters at trace levels, human urine constituting the major source of contamination. This study focussed then on the development and characterisation of molecularly imprinted polymers (MIPs) for the selective solidphase extraction of oxazepam at the trace levels from environmental water and human urine samples. Two MIPs were thus synthesized and their selectivity in pure organic and aqueous medium were assayed. After optimizing the extraction procedure adapted to a large sample volume to reach a high enrichment factor, the most promising MIP was applied to the selective extraction of oxazepam from environmental waters. Extraction recoveries of 83 ± 12, 92 ± 4 and 89 ± 10% were obtained using the MIP for tap, mineral and river water respectively while a recovery close to 40% was obtained on the corresponding non-imprinted polymer (NIP). Thanks to the high enrichment factors obtained, the LOQ was of 4.5 ng L-1 for river water. A selective extraction procedure was also developed for urine sample and gave rise to extraction recoveries close to 95% on MIP and of only 23% on NIP, which. Using the MIP, a LOQ of 357 ng L-1 for oxazepam in urine was obtained. The use of the MIP also allowed to limit matrix effects encountered for the quantification of the oxazepam in environmental samples and in human urine samples after extraction on Oasis HLB sorbent.