We have investigated the emission spectroscopy of allyl iodide, CH2=CHCH2I, and allyl alcohol, CH2=CHCH2OH excited at 199.7 nm. Ab initio calculations at the configuration interaction with single excitation (CIS) level indicate that the excited state accessed near 200 nm in allyl iodide has mixed electronic character with contribution from a pi --> Rydberg(16) configuration, a pi (C=C)/n(1) --> sigma*(C-I)/pi*(C=C) configuration, and a pi --> Rydberg(20) electronic configuration (where we have given the number of the Rydberg molecular orbital in parentheses). The emission spectrum is dominated by activity in the CH2 wag and the C=C stretch, reflecting the dynamics of the molecule in the Franck-Condon region of the excited state. The emission spectrum along with the ab initio calculations on the two conformers of allyl alcohol present at room temperature allow us to assign the transition at 200 nm to be mixed pi pi* character and pi --> Rydberg in character.