Field pea is one of the important short-duration cool season pulse crops which contributes significantly towards food and nutritional security. Two heat-susceptible (HS) and two heat-tolerant (HT) genotypes were selected from the previous study for further characterization. A significant variation was observed for morpho-physiological traits studied. Principal component analysis explained that first two principal components, i.e., PC1 and PC2 showed 76.5% of the total variance in optimal condition, whereas 91.2% of the total variance was covered by the first two PCs in heat stress environment. The seed yield per plant determined significant and positive association with superoxide dismutase and number of seeds per pod under optimal conditions, whereas under heat stress condition, it was positively associated with number of effective pods per plant, biological yield per plant, proline, pod length, number of seeds per pod, superoxide dismutase, and peroxidase. The significant reduction was noticed in the susceptible genotypes, whereas tolerant genotypes showed stable and non-significant reduction in chlorophyll content. Further, minimum cell damage and higher hydrogen peroxide production was noticed in the susceptible genotypes. In addition, the biochemical characterization of HS and HT genotypes revealed that the higher expression of peroxidase, superoxide dismutase, and catalase modulates the tolerant responses in HT genotypes. These genotypes were further used in developing heat-tolerant field pea genotypes.