The homogeneous solutions of meta-acrylates of Bi, Pb, Sr, Ca, Cu were synthesized, and by spray-pyrolysis of the solutions and following annealing the high temperature superconducting Bi2Sr2CaCu2Ox+Bi2Sr2Ca2Cu3Oxfilms were prepared on LaAlO3substrates. The connection was observed between annealing temperature, film thickness and type, quantity, and forms of impurity phases, such as strontium and calcium cuprates, calcium oxides, strontium oxides. The properties of these films (Ts≅ 81 K, ΔTs≅ 1 K) were shown to take place in case if their microstructure consisted of scale-like plates forming [001] texture. Also, it was concluded that under optimum conditions the Tscould be raised to > 100 K in Bi–containing films