Radioluminescence mapping using well-characterized and optimized optical systems is an effective method for localizing contamination with alpha-emitting radionuclides. To apply this novel approach to radiological emergency management, nuclear safeguards, nuclear decommissioning, and nuclear forensics, an established traceability chain is required. This work presents the development and implementation of a novel calibration methodology to provide valuable information about, and confidence in, the performance of radioluminescence detection systems. The proposed calibration methodology is based on two complementary approaches: (a) application of well-characterized activity standards to establish a traceable relationship between radioluminescence intensity and alpha activity, and (b) use of all optical radiation-based devices that, when calibrated against an alpha activity standard, simulate the radioluminescence induced in nitrogen (N2) and nitric oxide (NO) gases by alpha particles in specific spectral regions. A dedicated 210Po alpha activity standard with a narrow peak of less than 32keV FWHM at 5.3MeV has been developed and used to characterize a lens-based radioluminescence detection system in terms of its sensitivity to alpha-induced radioluminescence in different atmospheres (air, N2, N2 + NO mixture) in the UV-A and UV-C (solar blind) spectral regions. The characterized lens system was then used as an intermediary transfer device to cross-calibrate two portable integrating sphere-based radiance standards designed to simulate radioluminescence in the UV-A and UV-C spectral regions. Both radiance standards can be used as transfer standards simulating up to 510MBq when used in the UV-A and up to 8.7GBq when used in the UV-C spectral regions. They substantially simplify routine quality control of radioluminescence detection systems by eliminating the need for open alpha sources, which are always associated with strict radiation safety precautions. Furthermore, since radiance standards can operate in a wide range of intensities, linearity and detection limits of radioluminescence detectors can be readily determined. The design, construction, radiometric characterization, and calibration of dedicated transfer standards, as well as the development of new calibration procedures for radiometric traceability of radioluminescence detection systems, will enable appropriate accident and post-accident radiation measurements that will lead to more effective countermeasures and better protection of people, wildlife, and the environment.