Stacking of poly(3-alkylthiophene)s P3RThs and poly(4-alkylthiazole)s P4RTzs has been studied. Light scattering analysis indicates that head-to-tail (HT) type HT-P3HexTh (R = n-C6H13) gives a degree of depolarization (ρv) of 0.26 in CHCl3, which reveals that HT-P3HexTh takes a stiff structure even in the good solvent. Addition of CH3OH to CHCl3 solutions of HT-P3HexTh and head-to-head (HH) type HH-P4HepTz (R = n-C7H15) leads to π-stacking of the polymer molecules to form stable colloidal particles. The light scattering analysis of the colloidal solution of HT-P3HexTh in a 2:1 solution of CHCl3 and CH3OH reveals that HT-P3HexTh is aggregated in a parallel style. Results of filtration experiments using membranes with 0.20 and 0.02 μm pores agree with the degree of the aggregation. P3HexThs with irregular structures (P3HexTh (Fe) and P3HexTh (Ni) with HT/HH ratios of about 7/3 and 1/2, respectively) show a weaker trend to aggregate; however, P3HexTh (Fe) is considered to stack in a surface region of a stretc...