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A superconducting material with a composition Y1−xBa2Cu3O7−3/2x − x/2 Bi2O3 (x = 0·1 and 0·2) was synthesised. The influence of Bi2O3 additions on sintering was studied. Preliminary investigations of the Bi‐Sr‐Ca‐Cu‐O system were also made. Thick film pastes, prepared from Y1−xBixBa2Cu3O7 compositions, from the compound YBa2Cu3O7 with 10 w/o addition of Bi2CuO4 and from two compositions in the Bi‐Sr‐Ca‐Cu‐0 system, were fired on Al2O3 and ZrO2 substrates. All thick film materials based on YBa2Cu3O7 compound were superconducting at temperatures above 77 K when fired on ZrO2 substrates, while only a material with the starting composition Y0·8Ba2Cu3O6.7 − 0·1 Bi2O3 reached zero resistivity above 77 K on Al2O3 substrates. Tc (onset) of samples based on the YBa2Cu3O7 compound was around 95 K, and of samples from the Bi‐Sr‐Ca‐Cu‐O system between 95 and 100 K.