Liquid crystals (LCs) have been a vital component of modern communication and photonic technologies. However, traditional LC alignment on polyimide (PI) requires mechanically rubbing treatment to control LC orientation, suffering from dust particles, surface damage, and electrostatic charges. In this paper, LC alignment on organic single-crystal rubrene (SCR) has been studied and used to fabricate rubbing-free LC devices. A rubrene/toluene solution is spin-coated on the indium-tin-oxide (ITO) substrate and transformed thereafter to the orthorhombic SCR after annealing. Experimental result reveals that SCR-based LC cell has a homogeneous alignment geometry, the pretilt angle of LCs is low and the orientation of LCs is determined with capillary filling action of LCs. LC alignment on SCR performs a wider thermal tolerance than that on PI by virtue of the strong anchoring nature of LCs on SCR due to van der Waals and π-π electron stacking interactions between the rubrene and LCs. SCR-based LC cell performs a lower operation voltage, faster response time, and higher voltage holding ratio than the traditional PI-based LC cell. Organic SCR enables to play a role as weakly conductive alignment layer without rubbing treatment and offers versatile function to develop novel LC devices.