Poly(amic acid)s (PAAs) alignment agents have been prepared from the alicyclic dianhydrides, including 1,2,3,4‐cyclobutanetetracarboxylic dianhydride (CBDA, I), 1,3‐dimethyl‐1,2,3,4‐cyclobutanetetracarboxylic dianhydride (DMCBDA, II), and ester‐linked aromatic diamines, including 4‐aminophenyl‐4′‐aminobenzoate (APAB, a) and bis(4‐aminophenyl)terephthalate (BPTP, b), respectively. The derived PAAs, including PAA‐Ia (CBDA‐APAB), PAA‐Ib (CBDA‐BPTP), and PAA‐IIa (DMCBDA‐APAB) exhibited the preferable molecular weights, while the PAA‐IIb (DMCBDA‐BPTP) showed the low one due to the low polymerization reactivity both for the DMCBDA dianhydride and the BPTP diamine. All the PAA solutions except PAA‐IIb were adopted as the alignment components to fabricate liquid crystal (LC) minicells with a mode of in‐plane switching (IPS). The polyimides (PI) alignment layers derived from the thermal dehydration reaction of the PAA precursors at 230°C for 30 min showed good alignments effects to the LC molecules, which exhibited the pretilt angles (θp) from 0.09 to 0.15° after being exposed by the linear polarized ultraviolet light sources with the wavelength of 254 nm. In addition, the PI alignment layers afforded good optoelectronic features to the minicells, including the voltage holding ratio values over 97% at room temperature, and the residual direct circuit voltages lower than 1.0 V. The anchoring energy results indicated that the PI‐IIa (DMCBDA‐APAB) alignment layer showed the highest interaction with the LC molecules, and thus exhibited the highest threshold voltage (Vth) in the voltage‐transmittance (V‐T) measurements for the minicells.