The invention discloses a platinum-rhodium composite electrode for a nitrogen-oxygen sensor chip and a preparation method of the platinum-rhodium composite electrode. The platinum-rhodium composite electrode comprises a porous platinum-rhodium alloy electrode layer and a porous platinum electrode layer, wherein the porous platinum-rhodium alloy electrode layer and the porous platinum electrode layer are arranged on a double-layer three-dimensional catalytic net; the electrode slurry of the porous platinum-rhodium alloy electrode layer comprises the following components in parts by mass: 30-60 parts of nano platinum powder, 2-6 parts of a rhodium-containing compound, 1-2 parts of a protective agent, 8-20 parts of nano porous carbon powder, 0.1-1 part of a dispersing agent, 3-10 parts of an organic binder, 0.1-0.8 part of an organic zirconium compound, 0.01-0.4 part of an yttrium-containing compound, 0.01-0.6 part of a cerium-containing compound and 12-40 parts of an organic solvent. The platinum-rhodium composite electrode for the nitrogen-oxygen sensor chip and the preparation method of the platinum-rhodium composite electrode have the characteristics of high catalytic activity, good uniformity, excellent mechanical property, reliability, durability, long service life and low cost.