Polyimide aerogels display excellent mechanical strength, high thermal stability, low thermal conductivity, and outstanding dielectric properties. Typically, the synthesis of polyimide aerogels involves the polycondensation of dianhydride and diamine into poly(amic acid) (PAA) oligomers, which are then cross-linked and chemically imidized into polyimide. The stoichiometry of dianhydride and diamine determines the number of repeat units and length of the PAA oligomers, which in turn determines the cross-linking density. Despite the critical role of polymer concentration and number of repeating units in determining the microstructure and properties of polyimide aerogels, few detailed studies exist on these two parameters. Here, we synthesized and characterized 16 polyimide aerogel formulations from the common monomers biphenyl-3,3′,4,4′-tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA), with different repeat units (n = 5, 15, 30, 45) and total polymer concentrations (4, 7, 10, 13 wt%). An increased polymer concentration accelerated gelation and enhanced the mechanical performance of aerogels, but surprisingly, it also led to higher volumetric shrinkage during aging, solvent exchange, and supercritical drying (SCD). Specific surface areas (SSAs) reached a maximum at intermediate polymer concentrations. A shorter oligomer chain length, i.e., a higher cross-linking density, led to moderately higher SSAs (between 320 and 400 m²/g) and reduced shrinkage, resulting in lower densities for a given polymer concentration. The density dependence of the thermal conductivity exhibits a pronounced U-shaped curve with a minimum in thermal conductivity of 21–23 mW/(m·K) between 0.080 and 0.120 g/cm³, with somewhat lower values for more highly cross-linked aerogels. This systematic study of polyimide aerogels forms the basis for designing polyimide aerogels with tailored properties for targeted applications.