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The complexation behavior of pyridoxine hydrochloride with certain oxa- and thia-crown ethers in dimethylsulfoxide has been studied by conductometric and polarographic techniques. The vitamin is observed to form complexes with six-membered coronand rings of the crown ethers. The conductivity studies indicate 1:1 complex formation between the vitamin and the crown ether. The nature of the atoms (oxygen and sulpur) in the coronand ring is observed to affect the stability of the complex. The limiting ionic conductivity of the complexed vitamin is also reported. In addition, complexation studies of pyridoxine hydrochloride were carried out by polarography, and the results obtained compared well with those obtained by conductivity measurements.