Solution-processed polymer optoelectronic devices such as light-emitting diodes and solar cells have many advantages for large-area manufacture, and show increasing levels of performance. Here, we review recent progress in using blends of two conjugated polymers for optoelectronic devices. The blending of two or more polymers allows tuning of device performance, and for photovoltaics presents an attractive way to combine donor and acceptor materials with a morphology controlled by polymer phase separation. We discuss recent advances in imaging the microstructure of conjugated polymer blends, and we demonstrate how the blend structure leads to performance advantages in both LEDs and photovoltaic devices.