Biosensors are a rapidly growing research field, which is being swiftly advanced due to recent advances in nanotechnology. However most of the sensors developed are solution based, which limits their commercial use. Thus, with the view to developing bio-nanosensors based on solid-state photoluminescent nanofibres the electrospinning process was optimised for a novel PPV-derivative composite material. The electrospinning conditions for poly(dimethyl-6,6'-((2-((E)-2,5-bis(2-methoxyethoxy)-4-((E)-prop-1-en-1-yl)styryl)-5-methyl-1,4-phenylene)bis(oxy))dihexanoate) (PDBH) blended with PLGA or PLA were optimised. The PDBH composite electrospun mats were characterised by means of fluorescence microscopy and scanning electron microscopy (SEM). SEM images of the electrospun mats revealed a unique honeycomb morphology of the electrospun fibres due to the effects of a salt added and the PPV itself. The developed composite was suggested for further investigation into developing a novel, solid-state biosensor.