A process of blackening of electroless nickel coating is investigated to produce ultra black coating on titanium alloys with higher optical properties. Process optimization was carried out by investigating the influence of various operating conditions, namely, processing time of etching solutions, thickness of electroless nickel deposit, temperature of blackening solutions, and pH of electroless nickel solution on the physico-optical properties of the black coating. It was observed that an optimum thickness of 35 ? 5 lm of electroless nickel is required to achieve the ultra high optical properties after blackening. Energy dispersive X-ray spectroscopy studies suggested that films containing *7% phosphorous are good for further blackening. Scanning electron and optical microscopic studies confirmed that the surface morphology played the major role to get the ultra high optical properties. The environmental tests, namely, humidity, corrosion resistance, thermal cycling, thermo vacuum performance, and thermal stability tests were used to evaluate the space worthiness of the coating. Optical properties of the coating were measured before and after each environmental test to ascertain its stability. The blackened electroless nickel provides higher optical properties in the order of *0.85; this coating has good adhesion, uniformity, and stability in adverse space conditions. Hence, these coatings were extremely suitable for spacecraft thermal control applications.