The direct sampling of analytes from surfaces under atmospheric conditions followed by mass spectrometric analysis is an ever expanding area of scientific research. Atmospheric pressure surface sampling and ionization techniques for mass spectrometry (MS) offer the ability to interrogate samples that could not be studied under vacuum conditions required of more traditional MS surface analysis techniques. The geometry and nature of materials or surfaces that can be analyzed has been greatly expanded as a result. This dissertation characterizes and shows applications of liquid microjunction surface sampling probe (LMJ-SSP) electrospray ionization systems. The presented work compares traditional analytical work flows with novel analytical workflows utilizing LMJ-SSP-MS technology. The increase of throughput and/or chemical information without the sacrifice of analytical figures of merit is shown and discussed. The readout of analytical surfaces; surfaces where analyte has ended up on a surface in a traditional work flow and not just placed there, constitutes the focus of what is presented in the preceding work. Finally the prospects for spatial liquid chromatography-mass spectrometry (LC-MS) as a powerful analytical technology „in wait‟ is discussed and supported by the presented data.