In this Tutorial, we present an overview of the development of the photopyroelectric (PPE) technique from its beginning in 1984 to the present day. The Tutorial is organized into five sections, which explore both theoretical and experimental aspects of PPE detection as well as some important spectroscopic and calorimetric applications. In the “Introduction” section, we present the fundamental basics of photothermal phenomena and the state-of-the-art of photopyroelectric technique. In the “Theoretical aspects” section, we describe some specific cases of experimental interest, with examples in both back and front detection configurations. Several mathematical expressions for the PPE signal in specific detection modes (combined back–front configurations and PPE–thermography methods) are also deduced. The “Instrumentation and experiment” section contains two subsections. The first describes several examples of setups used for both room temperature and temperature-controlled experiments. The second subsection is dedicated to the configuration of detection cells and to the various sensor/sample assemblies that are currently used in spectroscopic and calorimetric experiments for both liquid and solid samples. The “Applications” section is in fact a collection of experimental results dedicated to the thermal characterization of a wide range of solid and liquid samples. At the end of this section, we present some examples that have been selected to convey that the PPE technique is not only useful in the investigation of optical and thermal properties of a variety of condensed matter samples, but also to study physical and chemical processes such as molecular associations, food adulteration, or phase transitions. In “Concluding remarks,” we summarize the advantages of this technique in spectroscopic and calorimetric applications.

An alternative photopyroelectric (PPE) technique that combines the front detection configuration (FPPE) with the thermal-wave-resonator-cavity (TWRC) method is proposed. The theoretical analysis of the phase of the FPPE signal indicates that the configuration offers information about both fluid sample and backing material. The backing independent values of the normalized PPE phase give the possibility to calculate fluid’s thermal diffusivity. By monitoring the thickness of a fluid with well known properties, the thermal effusivity of a solid sample (backing material) can be measured.

A new photopyroelectric detection configuration is proposed in order to measure the thermal effusivity of porous solids. Compared with the previously reported detection scheme this configuration makes use of a transparent window in front of the pyroelectric sensor. In such a way, the heat losses by convection at the sensor’s irradiated surface are eliminated, and consequently, the conduction remains the only process responsible for the heat propagation in the whole detection cell. In the paper, the mathematical model for this new configuration is developed, with the main conclusion that the sample’s thermal effusivity can be finally obtained via a fitting procedure with only two fitting parameters (instead of three as previously reported); in such a way, the possible degeneracy of the results is eliminated. The suitability of the method is demonstrated with application on some porous building materials and cellulose-based pressed powders.