A crucial polymer intermediate, 4-[1-(4-hydroxyphenyl)cyclopentyl]-phenol (bisphenol CP), was developed from dicyclopentadiene (DCPD), a key byproduct of the C5 fraction in petrochemicals. On the basis of bisphenol CP, a diamine, 4,4′-((cyclopentane-1,1-diylbis(4,1-phenylene))bis(oxy))-dianiline (cyclopentyl diamine; CPDA) was subsequently obtained through a nucleophilic substitution of bisphenol CP, followed by the hydrogenation process. By using the CPDA diamine, a series of polyimides with cyclopentyl (cardo) units on the backbone were prepared along with a reference polyimide (API-6F) based on 4,4′-(4,4′-(propane-2,2-diyl)bis(4,1-phenylene))bis(oxy)dianiline (BPAA), and 4,4′-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) for the exploration of structure-properties relationship. Thanks to the presence of cyclopentyl units, this type of cardo polyimides exhibited comparable tensile properties, especially a large elongation (25.4%). It is also worth noting that CPI-6F exhibited better solubility in organic solvents, such as NMP, DMAc, THF, and chloroform, than the other PIs. Gas separation properties were also evaluated for these cardo-type polyimides.