Hybrid lead halide perovskites have emerged as an attractive photoactive semiconductor for optoelectronic applications such as photovoltaics. However, their toxicity and stability issues pose significant challenges to its wide-scale applications and hence the need to find alternative perovskites that are stable and environmentally benign. Recently, double perovskites have been suggested as a potential alternative owing to their non-toxicity and high stability. In the present study, we report the first synthesis of Rb2AgBiI6 thin films in a cubic crystal structure using a facile room-temperature single-step solution process synthesis method and explore their potential optoelectronic applications. The structural, thermal, and mechanical stability, electronic, and optical properties are studied using various experimental techniques, and the results are further corroborated by first-principles density functional theory (DFT) calculations. The Rb2AgBiI6 film has an estimated band gap ∼ of 1.98 eV with the demonstrated thermal stability of ∼ 440 oC, suggesting its potential suitability for low-cost thin-film solar cells. The initial fabricated photovoltaic device without optimization of the synthesis conditions and device architecture show power conversion efficiency (PCE) of 0.1 % and an open-circuit voltage (Voc) of 0.46 V. The successful incorporation of Rb in Bi-based double perovskite should open the way to a new class of Rubidium-based perovskites with significant potential for optoelectronic applications.