Plasma gas-modified cyclo-olefin polymer (COP) surfaces and the interfaces between borosilicate glass and COP films were investigated by sum-frequency generation (SFG) vibrational spectroscopy. Upon exposure to oxygen gas plasma, the SFG signal intensities increased, indicating an improvement in the orientational order at the surface functional groups. In addition, thermal annealing following lamination improved the COP interphase molecular ordering and increased the number density of functional molecules at the interfaces.