Thermal and photochemistry of methyl iodide ($CH_3I);adsorbed;on;D_2O$ ice film on Cu(111) at 100 K were studied using temperature-programmed desorption (TPD) time-of-flight mass spectrometry (TOF-MS), X-ray and ultraviolet photoelectron spectroscopies. On the basis of TPD, multilayer and monolayer $CH_3I$ molecules desorb from $D_2O$ ice layer at 120 and 130 K, respectively. Photo-irradiation at 100 K exhibits dramatic changes in the TPD and I $3d_{5/2};XPS;of;CH_3I$ on ice film, due to a dramatic dissociation of $CH_3I$. The dissociation is likely activated by solvated electrons transferred from the metal substrate during photo-irradiation. No other photo-initiated reaction products were found within our instrumental detection limit. During photo-irradiation, the $CH_3I$, $CH_3$ and I could be trapped (or solvated) in ice film by rearrangement (and self-diffusion) of water molecules. A newly appeared parent molecular desorption peak at 145 K is attributed to trapped $CH_3I$. In addition, the $CH_3$ and I may diffuse through ice and chemisorb on Cu(111), indicated by TPD and I $d_{5/2}$ XPS taken with photo-irradiation time, respectively. No molecular ejection was found during photo-irradiation at 100 K. The work functions for $CH_3I/Cu(111),;D_2O/Cu(111);and;CH_3I/D_2$O/Cu(111) were all measured to be about 3.9 eV, 1.0 eV downward shift from that of clean Cu(111).