Gallium Arsenide (GaAs) is widely used as a material for fabricating devices such as high mobility transistors and laser diodes. Studies on the growth of GaAs layers have mainly been carried out using GaAs(100) substrates due to the maturity of (100) substrate technology. However, it has been reported that GaAs layers grown on GaAs(n11)A (n≤3) substrates have many advantages such as the amphoteric nature of a Si dopant, a high emission efficiency and the piezoelectric effect. In this article, we review techniques for growth on GaAs(n11)A substrates and properties of epitaxial layers. Furthermore, we also review applications to devices such as tunneling transistors and laser diodes.