•One pot of a simple solvothermal method has been used for the preparation of different polyacene quinone radical (PAQR) polymers.•The presented PAQR polymers with different conductivity are successfully obtained.•PAQR polymers exibit smart electrorheological behavior.Polyacene quinone radical (PAQR) polymers were synthesized by the step-growth condensation of aromatic hydrocarbon derivatives reacting with pyromellitic anhydride via a solvothermal method. The morphology and structures of PAQRs with varied polymerization processes were confirmed by the analysis of X-ray, IR, SEM and TG measurement. The effects of different aromatic hydrocarbons on the synthesis and morphology of PAQR polymers were investigated and then utilized as an electrorheological (ER) material by dispersion in silicone oil. The ER performances are investigated as a function of electric field strength by using a rheometer and the relationship between the conductivity and electrorheological (ER) properties of different polyacene quinone radical (PAQR) polymers were discussed.