AbstractNovel soluble polyimides containing perylene units have been synthesized. The polymers were prepared in a one‐step polycondensation reaction from 1,6,7,12‐tetrakis(4‐tert‐butylphenoxy)‐3,4:9,10‐perylenedianhydride and aliphatic and aromatic diamines. The amorphous polyimides have a very good solubility in a wide range of organic solvents and exhibit thermal stability up to 350°C. The polymers consist of 10 to 30 monomer units and show a narrow molecular weight distribution. The dark red materials can be used as polymeric dyes (absorption wavelength: λmax = 590–610 nm) and exhibit fluorescence near 620 nm.