Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications, such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior improved performance when compared with materials in a more disordered form. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. Here we report the first example of photoconductive behaviour of single-crystal charge-transfer interfaces. The system composed of rubrene and 7,7,8,8-tetracyanoquinodimethane presents a responsivity reaching 1 AW(-1), corresponding to an external quantum efficiency of nearly 100%. This result opens the possibility of using organic single-crystal interfaces in photonic applications.