The cocrystallization of alkylated polyimides and polyesters, as shown by Ballauff et al., offers an opportunity to mix alkylated electrically conducting blends with the alkylated insulating materials, In this investigation we have used a flexible alkylated polymer to blend with a stiff alkylated conducting polymer. Comb-shaped poly(octadecyl acrylate) (PODA) was blended with polyaniline emeraldine base (PANI)/dodecyl benzenesulfonic acid (DBSA) complex to investigate the effect of long alkyl chain of flexible polymer on the electroactive rigid rod-like PANI(DBSA)(4) (weight ratio) complex, Binary blend DBSA/PODA was also used as a model to investigate the intermolecular interaction between unprotonated excess amounts of DBSA and PODA in the ternary blend, Cross-polarized optical microscope (OM) and wide-angle X-ray diffraction (WAXD) were applied to observe the highly ordered mesophase structure of these blends. This newly formed mesomorphic structure of DBSA/PODA binary blend due to the hydrogen bonding was observed when the PODA content was below 40 wt% in binary blend and these blend samples show a homogeneous one phase above 68 degrees C by OM. With addition of 10 wt% of PODA in ternary blend, the homogeneous smectic liquid crystalline structure was clearly confirmed by OM and WAXD. The intermolecular interactions that occurred in the blend systems was explained for each different characteristic peak with FT-LR spectra.