Photopyroelectric spectroscopy was used for thermal characterization of the solvent diethylene glycol dimethyl ether (Diglyme). Photopyroelectric detection is based on the measurement of an electrical signal due to temperature variations in a pyroelectric detector. In this work, two configurations of the photopyroelectric technique were used. The sample thermal diffusivity (α_s) was measured by using the thermal-wave resonator cavity (TWRC) configuration and the thermal effusivity (e_s) was obtained by using the inverse photopyroelectric (IPPE) configuration. From the obtained values of α_s and e_s the thermal conductivity (k) and heat capacity per unit volume (ρc) were calculated through the relationships k = e_s (α_s)^1/2 and ρc = e_s/(α_s)^1/2. On comparing the obtained k value for the Diglyme sample with some reference data reported in the literature, it was found that the reported k value for diethylene glycol diethyl ether (compound with a similar structure to Diglyme) is similar to the obtained k value for Diglyme in the present study. To our knowledge the thermal characterization of Diglyme has not been reported until now.