Stable regular honeycomb structures of various polypyrroles having a stick width of 50 mu m and a structure height of 110 mu m were formed by the electropolymerization of pyrrole or substituted pyrrole in aqueous solutions at high current densities. The advantages of these microstructures in sensories and spectroelectrochemistry are shown for specific applications. The high electrical conductivity and the stability of the polymer were attained using aromatic sulfonate derivatives as electrolytes. Regular honeycomb structured polymer electrodes with channels of 50 mu m were prepared and used for electrochemical and spectroelectrochemical studies. The cation-exchange properties of such structures were tested by Al3+ ions. The preparation of PPy-LIGA structures with specific groups was demonstrated by copolymerization of pyrrole with pyrrole-2-carboxylic acid. The high sensitivity and specificity of ESR signal of PPy-LIGA structures to the oxygen was observed.