Good film formation is one of basic requirements for organic optoelectronic materials to achieve the capability for fabrication of large area devices. Small molecular optoelectronic compounds have a definite chemical structure and clear device performance, and thus are welcomed in the field. However, they are generally suffering from poor film formation, especially in a large area. For addressing it, this contribution proposes and demonstrates a strategy, that is, changing them into poly(rod-coil) polymers. With one optoelectronic compound [BDT(DTBT)(2)] and three poly(rod-coil) polymers (P1, P2, and P3) having different non-conjugated coil segments as examples, the work clearly shows that the change to poly(rod-coil) polymers keeps many basic optoelectronic properties of the reference compound, including light absorption in solution, bandgap and frontier orbital energy levels, but suppresses strong intermolecular interactions and crystalline structure in film state. Further comparisons on film formation quality on glass and ITO glass illustrate that all the three polymers have a better film formation property than the reference compound.