Luminescent semiconducting oligomers (LSOs) have been one of the most popular molecular materials that can be applied in various fields due to its distinctive optical properties. The study of molecular packing and morphological change of oligomers is essential for the rational design of materials and regulation functions. Herein, we report two novel LSOs (OFBB and OFBT) with a slight difference in chemical structures but show distinct different self-assembly behaviors in the coordination-driven process. OFBB forms spherical particles with Zn(II). Compared with OFBB, OFBT has additional thiazole moiety, which forms spherical particles with Zn(II) and then transforms to crystalline nanobelt in two hours. The process and mechanism of the nanospheres and nanobelts formation were investigated in detail. The double S•••N interaction between two benzothiazoles in adjacent oligomers played a significant contribution in this dynamic morphology transformation. In addition, the as-prepared two products showed excellent sensing toward nitrobenzene with good selectivity over other nitroaromatic explosives.