A new class of conjugated polyacetylenes having perylene bisimide units and pendant fullerene or porphyrin groups were synthesized and characterized. SEM images displayed the aggregation superstructures of two polymers. The poly(5(0.1)-co-4(0.9)) can form a large quantity of spherical nanoparticles in chloroform because [60]fullerene derivatives have high aggregation tendency due to the π-π* stacking of the carbon cage. Furthermore, poly(6(0.1)-co-4(0.9)) can form different aggregation structures in chloroform with the addition of 4,4'-bipyridine (Bipy). In particular, when poly(6(0.1)-co-4(0.9)) was mixed with 2 equiv of Bipy, a uniform cottonlike superstructure was observed. These results indicated that the axial coordination of zinc porphyrin and Bipy played an important role in controlling the aggregation morphologies of poly(6(0.1)-co-4(0.9)) in CHCl3 with the addition of Bipy. More interestingly, the photocurrent measurement showed that the films of these polyacetylenes could produce steady and rapid cathodic photocurrent responses, indicating that efficient charge transfer took place in two donor-acceptor polymers.