In this report, we explore the optoelectronic properties of a low band-gap copolymer based on the alternation of electron rich (thiophene and thienothiophene units) and electron deficient units (pyridal[2,1,3]thiadiazole (Py)). Initial density functional theory calculations point out the interest of using the Py unit to optimize the polymer frontier orbital energy levels. A high molecular weight (Mn = 49 kg/mol) solution-processable copolymer, based on Py, thiophene and thienothiophene units, has been synthesized successfully. From cyclic-voltammetry and UV–visible absorption measurements a relatively deep HOMO level (−5.1 eV) and an optical band-gap (1.48 eV) have been estimated. Charge transport both in horizontal and vertical directions were extracted from field-effect transistors and space charge limited current diodes, respectively, and led to a relatively high in-plane hole mobility in pure polymer films (0.7 × 10−2 cm2 V−1 s−1). GIWAXS results showed almost identical in-plane lamellar morphologies, with similar average size and orientation of the polymer crystalline domains in both, pure polymer films and polymer:fullerene blends. Also, the gate-voltage dependence of the field-effect mobility revealed that the energy disorder in the polymer domains was not altered by the introduction of fullerenes. The nevertheless significantly higher out-of-plane hole mobility in blends, in comparison to pure polymer films, was attributed to the minor amorphous polymer phase, presumably localized close to the donor/acceptor interface, whose signature was observed by UV–vis absorption. Promising photovoltaic performances could be achieved in a standard device configuration. The corresponding power conversion efficiency of 4.5% is above the value achieved previously with a comparable polymer using benzo [2,1,3]thiadiazole instead of Py as acceptor unit.