Comparative analysis of macroscopic mechanical properties of a biodegradable polymer polypropylene carbonate (PPC) is carried out concerning two most commonly used, non-biodegradable synthetic polymers-high-density polyethylene (HDPE) and linear-low density polyethylene (LLDPE). Responses of the films of these polymers when subjected to mechanical and thermal stresses are analyzed. Response to tensile stress reveals the highest elongation at break (EB) in PPC films (396 ± 104 mm), compared to HDPE (26 ± 0.5 mm) and LLDPE (301 ± 143 mm), although the elastic modulus (YM) of PPC is around 50 ± 6 MPa, 3-fold lesser than LLDPE (YM = 153 ± 7 MPa) and 6-fold lesser than HDPE (YM = 305 ± 32 MPa). The plastic deformation response of PPC is intermediate to that of HDPE and LLDPE; initial strain softening is followed by strain hardening in LLDPE, a plateau region in PPC, and prolonged strain softening in HDPE. Crystalline domains in HDPE produce restriction on molecular motion. Crystallinity abruptly decreases by 70% in HDPE following a thermal quench, showing the possibility of free chain molecular mobility during plastic deformation. High correlation among Raman modes for all polymers reveals cooperative relaxation processes after thermal quench; C-C stretching modes and C-H bending, CH2wagging modes have Pearson's correlation coefficient 0.9. The integrated peak intensity and width of the C-C stretching Raman mode is 3-fold higher in PPC than HDPE after a thermal quench, showing enhanced molecular mobility and contributing modes in PPC. The peak width of this mode shows a strong negative correlation of -0.7 with the YM and a strong positive correlation of 0.6 with EB, showing that higher amorphicity leads to enhanced molecular mobility and EB at the cost of YM. This study reveals importance of molecular-scale response in governing the macroscopic properties of polymers.