Given the recent rate of progress in artificial intelligence (AI) and robotics, a tantalizing question is emerging: would robots controlled by emerging AI systems be strongly aligned with human values? In this work, we propose a scalable way to probe this question by generating a benchmark spanning the key moments in 824 major pieces of science fiction literature (movies, tv, novels and scientific books) where an agent (AI or robot) made critical decisions (good or bad). We use a state-of-the-art LLM's recollection of each key moment to generate questions in similar situations, the decisions made by the agent, and alternative decisions it could have made (good or bad). We then measure an approximation of how well models align with human values on a set of human-voted answers. We also generate rules that can be automatically improved via an amendment process in order to generate the first Sci-Fi inspired constitutions for promoting ethical behavior in AIs and robots in the real world. Our first finding is that modern LLMs paired with constitutions turn out to be well-aligned with human values (95.8%), contrary to unsettling decisions typically made in Sci-Fi (only 21.2% alignment). Secondly, we find that generated constitutions substantially increase alignment compared to the base model (79.4% to 95.8%), and show resilience to an adversarial prompt setting (23.3% to 92.3%). Additionally, we find that those constitutions are among the top performers on the ASIMOV Benchmark which is derived from real-world images and hospital injury reports. Sci-Fi-inspired constitutions are thus highly aligned and applicable in real-world situations. We release SciFi-Benchmark: a large-scale dataset to advance robot ethics and safety research. It comprises 9,056 questions and 53,384 answers generated through a novel LLM-introspection process, in addition to a smaller human-labeled evaluation set.