A novel optical sensor has been proposed for sensitive determination of thorium (IV) ion in aqueous solutions. The thorium sensing membrane was prepared by incorporating 4-( p-nitrophenyl azo)–pyrocatechol (NAP) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to thorium ion by changing color reversibly from yellow to red-brown in glycine buffer solution at pH 3.5. The proposed sensor displays a linear range of 8.66 × 10 −6–2.00 × 10 −4 M with a limit of detection of 6 × 10 −6 M. The response time of the optode was about 8.8–12.5 min, depending on the concentration of Th (IV) ions. The selectivity of optode to Th (IV) ions in glycine buffer is good. The sensor can readily be regenerated by exposure to a solution mixture of sodium fluoride and 5-sulfosalicylic acid (dihydrate) (0.01 M each). The optode is fully reversible. The proposed optode was applied to the determination of thorium (IV) in environmental water samples.