Extensive all-atom molecular dynamics studies of polyethylene glycol (PEG2000) when solvated and in the polymer bulk condensed phases were performed across a wide temperature range. We proposed two modified all-atom force field and observed the fate of the PEG2000 macromolecule when solvated in water, water with 4% ethanol, and ethyl acetate. In aqueous solutions, the macromolecule collapsed into a prolate spheroidal ball-like structure while adopting a rather elongated coiled structure in ethyl acetate. Inspection of the polymer-condensed phases across the 150-340 K temperature range enabled the atomistic view of the solid glass below the glass transition temperature of 230 K < Tg < 250 K and the rubber behavior above Tg. Predicted properties include the enthalpy, density, and cohesive energy temperature behavior, the specific heat, thermal expansivity, thermal compressibility, bulk modulus, and Hildebrand solubility parameter both below and above Tg. Within the polymer matrix, the PEG2000 macromolecules were entangled displaying a wide distribution of sizes that persisted when transitioning from the glass to the rubbery phases. Calculated properties agree very well with experiments when available or stand as crucial predictions while awaiting experimental measurement. Understanding the thermodynamics and structure of this useful polymer enables the efficient prediction of its behavior when building novel composite materials for nanomedicine and nanotherapeutics.