Over the past decade ABX3 halide perovskites based on Pb have emerged as a most-promising class of materials. To-date they have been employed for record-breaking solar-cells, highly-efficient lightemitters, new photo-catalysts and even as X-ray detectors. A2BX6 vacancy ordered double perovskites (VODP) are air-stable and environmentally friendly (Pb-free) that have been proposed as alternatives, to halide perovskites. Yet, VODP materials have not achieve the high performance of their Pb-based counterparts. In this work, we thoroughly analyze the properties of the VODP family of materials by employing state-of-art ab initio calculations to unveil the key details of the electronic structure and the effects of electron-hole coupling on the optical properties.