Aromatic polyimides are interesting materials since they possess outstanding key properties such as thermoxidative stability, high mechanical strength, high modulus, excellent electrical properties, and superior chemical resistance. However, their low solubility makes them difficult to characterize, process and obtain high molecular weight polymer. In this report, we synthesized a series of precursor polymers that contains Diels-Alder (DA) adducts of anthracene. Different dienophiles were tried. These precursor polymers are soluble in common organic solvents such as chloroform and can be easily processed to thin films. Heating the film above 215 degree induce retro-DA reaction, which generated the fully aromatic polyimides in situ. The solid-state retro-DA reactions were monitored by ATR-FTIR and UV-Vis spectra. The fully aromatic polyimides are highly stable and their thin films are insoluble in organic solvents. Profilometry and AFM studies showed that after the thermal treatment, the films are smooth and pin-hole free, while the volumes decreased with a percentage close to the weight loss caused by retro-DA reaction. These Polymers can have a wide range of potential applications from thermal patterning polymers to organic photovoltaics.