In present work we reported the synthesis of polypyrrole in the presence of water-soluble azocalix[4]arene which obtained from diazo coupling reaction between calix[4]arene and diazonium salts. Azo groups bring to calixarenes a chromogenic activity.The (5,11,17,23-tetrakis[(p-carboxyphenyl)azo]25,26,27,28 tetra hydroxy calix[4]arene) was used as dopant anion. The effect of the content of azocalix[4]arene onto properties of polypyrrole was investigated. Polypyrrole/azocalix[4]arene salts were characterized by FTIR, TGA, SEM and conductivity measurements. The conductivity of polypyrrole increased in the presence of azocalix[4]arene. TGA results indicated that the polypyrrole/azocalix[4]arene salts have higher thermal stability than PPy. It was observed from SEM analysis that the particle diameter of PPy decreased with increasing content of azocalix[4]arene.