Olanzapine (OLP), chemically known as 2-Methyl-10-(4-methyl-piperazin-1-yl)-4H-3-thia-4, 9-diaza-benzo[f]azulene, is an atypical antipsychotic drug. It is used for the treatment of schizophrenia and bipolar disorder. A new simple and selective membrane based potentiometric sensor was developed for potentiometric determination of olanzapine. The membrane was constructed using an ion-pair of OLP and sodium tetraphenyl boron in dioctyl phthalate and PVC. The membrane provides good linear Nernstian response covering relatively wide concentration range of 4 × 10-6 - 1 × 10-2 M OLP over pH range of 2.6 - 7.8. The detection limit for the developed sensor was founded as 2.02 × 10-6 M. The response time of developed sensor is <10 s for the range of determination. The sensor showed good selectivity for OLP in the presence of various cations, anions and other organic molecules. The membrane was successfully applied in direct potentiometric determination of OLP in tablets. The percentage recovery of OLP, ranged from 96.2 to 99.68% with a mean standard deviation <5%, indicates the adoptability of sensor for the direct estimation of OLP in pharmaceuticals. The developed sensor was used to determine OLP in spiked human urine sample and the satisfactory results were obtained.