An understanding of the structure-function relationships of conjugated polymers is an invaluable resource for the successful design of new materials for use in organic electronics. To this end, we report the synthesis, characterisation and optoelectronic properties of a range of new alternating copolymers of dibenzosilole. Suzuki polycondensation reactions were used to afford a series of eight conjugated materials by the respective combination of either a 3,6- or 2,7-linked 9,9-dioctyldibenzosilole with 3,6-linked-N-octylcarbazole, triarylamine, oxadiazole and triazole monomers. The copolymers were fully characterised using 1H, 13C{1H} NMR spectroscopy, size exclusion chromatography (SEC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The photophysical properties were determined using UV-Vis spectroscopy, photoluminescence (PL) measurements, cyclic voltammetry (CV) and photoelectron emission spectroscopy in air (PESA). The spectroscopic and electrochemical measurements were used to determine the materials' HOMO and LUMO energies and the values were correlated with the copolymer composition and structure. A selection of the copolymers (P4, P5 and P8) were evaluated as the active layer within single-layer polymer light emitting diodes (PLEDs), with the configuration: glass/ITO/PEDOT:PSS/emissive layer/Ba/Al, which gave low intensity electroluminescence. The selected copolymers were also evaluated as the organic semiconductor in bottom-gate, bottom-contact organic field effect transistors (OFETs). The best performing devices gave a maximum mobility of 3 [times] 10-4 cm2 V-1 s-1 and on/off current ratios of 105.