In this work, the luminescent species present in flame front at combustions of ethanol and acetylene, in a long tube and without the air influence, were mapped. The flame emission was analyzed from 300 to 600 nm, with steps of 50 nm, and at 306.4, 431.3 and 516.5nm, corresponding to the emission maxima of OH, CH and C-2 excited radicals. Three gaseous mixtures with partial pressures of 2.00 kPa acetylene with 7.20 kPa oxygen, 4.53 kPa acetylene with 4.67 kPa oxygen, and 3.33 kPa ethanol with 6.67 kPa oxygen were studied. The results show that the fuel enrichment in the combustion of acetylene/O-2 enhanced the concentration of the C-2 excited radical relative to the concentrations of OH and CH excited radicals in the flame front. For the combustion of fuel-rich mixtures of ethanol/O-2 the main species in the flame front was the CH excited radical.