In situ temperature-dependent laser-induced photoluminescence and dielectric measurements provide new evidence for the local occurrence of the α → β phase transition near 500 K in the preserved crystalline parts of natural radiation-damaged titanite (sample E2335 with ∼24% amorphous fraction, containing Fe and Al impurities). Photoluminescence spectroscopic measurements show an anomaly in the vicinity of 500 K. The temperature-dependent evolution of the real part of the electrical conductivity (σ) and the real (ϵ′) and the imaginary (ϵ″) part of the complex dielectric permittivity (ϵ∗) of titanite have been measured at various AC frequencies (∼1.2-96.8 kHz). Despite the masking and smearing effect of impurities and defects, the temperature-dependent behaviour of ϵ′ and ϵ″ around the transition temperature of the investigated natural titanite E2335 shows a remarkable similarity to that of the synthetic end-member material (see Zhang et al (1995 Phys. Chem. Miner. 22 41-9)). This study indicates the suitability of photoluminescence and impedance spectroscopy for the detection of phase transitions, even in heavily disordered systems.