Vibrational spectroscopy and core-level photoelectron spectroscopy are two of the most powerful tools for surface chemical analysis. We have used both techniques in conjunction with others to study hydrocarbon radical interactions with metal and semiconductor surfaces as well as thin film deposition processes. These include the investigations of CH2 and CH3 reactions on Cu by high resolution electron energy loss spectroscopy (HREELS), and GaN formation from Ga(CH3)(3) and NH3 on SiC by SR-PES. The vibrational analysis has revealed rich surface chemistry of the radicals while the photoemission study has led us to develop new approach for probing ultrafine structures. The effort involves the construction of a scanning photoemission spectromicroscope (SPEM) coupled to a synchrotron radiation light source. Recent results are presented in this brief report.