I loved the Saturn 5, and it did have a perfect record for astronaut safety, but as I recollect it only had 10 manned flights, Apollo 8 through Apollo 17. I wonder how it would have fared over 100 flights. You also have to take into account that each Saturn 5 was brand new, unlike the shuttles, which are approaching 20 years old now. The Saturn had an escape system though, and if it did have a catastrophic failure the crew would have a chance of escaping with their lives, unlike the shuttle crews. I have gut feeling though, that if it had flown 100 or 500 times there was enough safety margin in the Saturn 5 that not one astronaut would have died as a result of it failing. The big difference is while the Saturn 5 could afford a catastrophic failure and still have the crew survive the shuttle can not.
Shuttle vs. Saturn 5
