The discovery of an orange flame is reported that appears also at higher pressures of active nitrogen and oxygen without the presence of a metal catalyst unlike previous research in over 30 years. Enhancement of emissions of the first positive band system of nitrogen was observed from various vibrational levels of the N-2(B (3) Pi(g)) state. Arguments to identify the species responsible and implications to previous research of this phenomenon of homogeneous excitation and collisional intersystem crossing into N-2(B (3) Pi(g)) induced by excited O-2 are presented. Its probing for lasing is suggested.