A kind of soluble and low-molecular polyimide was obtained from 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 3,3′-dimethyl-4,4′-diaminodiphenylmethane (DMMDA) with N,N-dimethylformamide (DMF) as solvent by a two-step method, and it could be dissolved both in strong polar solvents and in common low-boiling-point solvents. The ordered porous films were prepared by spreading the solution on solid substrate using water droplets as templates, and the pore size was about 1 μm. Furthermore, several influencing factors on the morphologies of the ordered pores, such as the concentration of the solution, solvents, and the solid substrates, were investigated. Fabrication of ordered microporous films from a kind of low-molecular polymer, with the number-average molecular mass (Mn) of 50433, was reported for the first time in this study. The results showed that the best-ordered pattern with strong periodicity, regularity, and a large, defect-free area could be formed from the polyimide with concentration of 50 mg/mL using dichloromethane as solvent and silicon as substrate.