This paper is based on a lecture Navrotsky gave honouring the memory of Paul McMillan. It summarizes our recent findings in the thermodynamics of hybrid materials including metal organic frameworks (MOFs), polymer-derived ceramics (PDCs) and ionic organic–inorganic compounds. This work describes the main structure types and their corresponding thermodynamic stability, obtained from calorimetric measurements in our laboratory. The effects of linker substituent and framework topology on the thermodynamic stability of isostructural zeolitic imidazolate frameworks and other MOFs are discussed. The paper documents the effects of interdomain interaction and bonding speciation on the thermodynamic stability of various PDC compositions, including SiC, SiOC and SiCN systems. The paper further describes effects of different cations on the thermodynamic stability of selected ionic organic–inorganic compounds. Similarities and differences among these materials are emphasized.This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 2)'.