Lead chalcogenides are the promising thermoelectric (TE) materials having narrow band gap. The present work investigates the TE behaviour of PbSe in the temperature range 300–500 K. The transport properties of the sample have been studied using the Abinit and BoltzTrap code. The experimentally observed value of S at 300 and 500 K is found to be ∼ 198 and 266 μ V K −1 , respectively. The rate of increase in S from 300 to 460 (460 to 500) K is found to be ∼ 0.4 (0.09). The temperature dependent electrical conductivity ( σ ) shows the increasing trend, with values of ∼ 0 . 35 × 10 3 and ∼ 0 . 58 × 10 3 Ω − 1 m −1 at 300 and 500 K, respectively. Further, the value of thermal conductivity ( κ ) at 300 (500) K is found to be 0.74 (1.07) W m −1 K −1 . The value of κ is found to be increasing upto 460 K and then starts decreasing. The dispersion plot indicates that PbSe is a direct band gap semiconductor with band gap value of 0.16 (0.27) eV considering spin–orbit coupling (without SOC). The partial density of states (PDOS) plot shows that Pb 6p and Se 4p states have a major contribution in the transport properties. The observed and calculated values of S gives a good match for SOC case. The calculated σ and electronic part of thermal conductivity ( κ e ) gives good match with the experimental data. The maximum power factor (PF) value of ∼ 4 . 3 × 10 −5 W/m K 2 is observed at 500 K. The room-temperature lattice thermal conductivity, calculated using the Slack equation, is found to ∼ 3.5 W m −1 K −1 . This work helps in understanding the TE behaviour of PbSe through a novel and insightful alliance of experimental measurements and DFT approach. • Understanding the experimentally observed thermoelectric parameters of PbSe using density functional theory approach. • Band structure shows that PbSe is a direct band gap semiconductor. • The inclusion of spin orbit coupling gives better match between experimental and computationally observed values. • Power factor increases with the rise of temperature.