Biaxially stretched composite polyethylene naphthalate (PEN) films (BSCPF) embedded with submicron lithium fluoride (6LiF) particles and luminescent molecules were fabricated to make large area scintillation films (≈1 m × 1 m) for thermal neutron detection. BSCPF had 20.2% higher neutron light yield as compared to unstretched composite film (UCPF), and were 2.46 ± 1.47 times more efficient for detecting thermal neutrons than lithiated glass GS20 above lower level discriminator corresponding to an intrinsic efficiency for gamma <10−6. MCNPX simulations for a layered BSCPF detector resulted 6.1 cps for 1 ng 252Cf, thus meeting the Pacific Northwest National Laboratory criteria for absolute neutron detection efficiency and intrinsic gamma-neutron discrimination. BSCPF have alpha to beta ratio of 0.25, which is higher than that for UCPF (0.11), and also for GS20 (0.22), which offers the possibility of excellent neutron/gamma discrimination.