Several organic–inorganic hybrid materials from the metal–organic framework (MOF) family have been shown to form stable liquids at high temperatures. Quenching then results in the formation of melt-quenched MOF glasses that retain the three-dimensional coordination bonding of the crystalline phase. These hybrid glasses have intriguing properties and could find practical applications, yet the melt-quench phenomenon has so far remained limited to a few MOF structures. Here we turn to hybrid organic–inorganic perovskites—which occupy a prominent position within materials chemistry owing to their functional properties such as ion transport, photoconductivity, ferroelectricity and multiferroicity—and show that a series of dicyanamide-based hybrid organic–inorganic perovskites undergo melting. Our combined experimental–computational approach demonstrates that, on quenching, they form glasses that largely retain their solid-state inorganic–organic connectivity. The resulting materials show very low thermal conductivities (~0.2 W m⁻¹ K⁻¹), moderate electrical conductivities (10⁻³–10⁻⁵ S m⁻¹) and polymer-like thermomechanical properties. [Figure not available: see fulltext.]