The nickel-aluminum (Ni/Al) intermetallic system is useful for a variety of reactive material applications, and reaction characteristics are well studied at the normal self-heating rates of 103–106 K/s. Recent experiments at 1011–1012 K/s have measured the kinetic energy of material ejected from the reaction zone, indicating additional kinetic energy from the reactive system despite high heating rates. In order to better probe reaction phenomena at these time scales, and determine the presence of expected elements and their temperatures, we report on emission spectroscopy of electrically heated, patterned Ni/Al bridge wires, time resolved over 350 ns through the use of a streak camera. Unlike previous studies where emission was dominated by Ar and N from residual gasses in the vacuum test chamber, here we report on experiments with encapsulated laminates allowing better quantification of Al and Ni emission. We were able to identify all major spectral lines from the dominant elements present in the films, and found the multilayered Ni/Al laminates to exhibit a brighter and longer duration emission than either Al or Ni control samples. We also found the measured electrical energy absorption of the Ni/Al laminates to follow that of the Al samples up to 150 ns following the onset of emission, indicating that the exothermic mixing of vapor phase Ni and Al was the most likely source for the higher emission intensity. These results will be important for new, energetically enhanced, high efficiency bridge wire applications, where shock initiation of subsequent energetic reactions may be accomplished with less electrical energy than is currently required.