Ordering of cations is important for controlling properties of ABO₃ perovskites, and CaFeFeNbO₆ is the first example of an Fe-based AA’BB’O₆ double double perovskite, with Ca²⁺/Fe²⁺ ordered on A-site columns, and Fe³⁺/Nb⁵⁺ at the octahedral B-sites. Substantial (37%) antisite disorder of the latter cations leads to spin glassy magnetism below a freezing transition at 12 K. The CaMnFeNbO₆ analogue also shows substantial cation disorder and spin glassy behaviour. Comparison of synthesis pressures for ordered materials based on different A-site transition metals, suggests that pressures of at least 14–18 GPa will be required to discover the expected plethora of double double perovskites based on A’ cations smaller than Mn²⁺.