Over the years, many famous personalities have signed the Golden Book of the state capital Mainz. These include federal presidents, the prime ministers of the state of Rhineland-Palatinate, heads of state, and even the Queen of England and Pope John Paul II.

• 1965 Jockel Fuchs
• 1968 Willy Brandt
• 1969 Dr. Gustav Heinemann
• 1970 Dr. Carl Zuckmayer
• 1971 Herbert von Karajan
• 1974 Dr. Helmut Kohl
• 1975 Dr. Walter Scheel
• 1978 Queen Elizabeth II
• 1978 Valentina Chagall (wife) representing Marc Chagall
• 1980 Prof. Dr. Karl Carstens
• 1980 Pope John Paul II
• 1984 Dr. Richard von Weizsäcker
• 1989 George Bush
• 1993 Rudolf Scharping
• 1994 Mikhail Gorbachev
• 1995 Prof. Dr. Roman Herzog
• 2000 Johannes Rau
• 2000 Kurt Beck
• 2001 Cardinal Karl Lehmann
• 2002 Hans-Dietrich Genscher
• 2004 FSV Mainz 05
• 2005 George W. Bush and Gerhard Schröder
• 2008 Lech Walesa