In order to characterize the free volume of a homologous series all-aromatic poly(ether imide) (PEI) membranes, two positron annihilation techniques were utilized: positron annihilation lifetime spectroscopy (PALS) and Doppler broadening (DB) of annihilation radiation. First, DB, which is a fast and convenient method, indicated differences in free volume of all PEIs investigated, whereas PALS experiments gave more quantitative information, with respect to the size and distribution of the voids. DB results show that S, W pairs for this PEI-series tend to group according to their dianhydride moiety, meaning that, in this series, dianhydrides govern the differences in the S parameter, indicating more free volume with increasing S value. The semicrystalline PEI samples exhibit the lowest S parameter, while the amorphous samples based on 3,3′,4,4′-oxydiphthalic dianhydride (ODPA) all lie on the higher S side of the S-W plot. With the 1,4-bis(4-aminophenoxy)benzene (P1)-based PEI (ODPA-P1) standing out with the highest S parameter. The same could be confirmed and quantified by PALS, where ODPA-P1 is the only membrane in this series with its free volume described by both smaller and larger free-volume elements. The larger voids in ODPA-P1 can be characterized as having a radius (R) of 3.3 Å, which is 5 times larger than the lowest measured free-volume content in this series observed for 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 1,3-bis(4-aminophenoxy)benzene (M1)-based PEI (BPDA-M1), which has voids with a radius of R ≈ 0.7 Å. When comparing results obtained by DB and PALS, a very good correlation is observed between the S parameter (determined by DB) and the free-volume content (quantified by PALS).