A new pyrrole-based conjugated oligomer (P1) was obtained with phenyl-linked triphenylamine moieties as an isolation group. Little aggregations were observed whether oligomer P1 was absorbed on titanium dioxide (TiO2) surface or in solid state. Since the pyrrole-based moieties in donor-π-acceptor type was the core component of oligomer P1 for light absorption, the corresponding dye-sensitized solar cell (DSSC) demonstrated the efficiency of light-to-electrical conversion by 0.48%. Higher conversion efficiency could be achieved by tuning the size of the isolation groups and the structure of the donor-π-acceptor type dyes.