Making accurate and reliable measurements of solar irradiance is important for understanding performance in the photovoltaic energy sector. In this paper, we present design details and performance of a number of fibre optic couplers for use in irradiance measurement systems employing remote light sensors applicable for either spectrally resolved or broadband measurement. The angular and spectral characteristics of different coupler designs are characterised and compared with existing state-of-the-art commercial technology. The new coupler designs are fabricated from polytetrafluorethylene (PTFE) rods and operate through forward scattering of incident sunlight on the front surfaces of the structure into an optic fibre located in a cavity to the rear of the structure. The PTFE couplers exhibit up to 4.8% variation in scattered transmission intensity between 425 nm and 700 nm and show minimal specular reflection, making the designs accurate and reliable over the visible region. Through careful geometric optimization near perfect cosine dependence on the angular response of the coupler can be achieved. The PTFE designs represent a significant improvement over the state of the art with less than 0.01% error compared with ideal cosine response for angles of incidence up to 50°.