Positive and negative ion mass spectra of organic polymers were recorded using the Laser Microprobe Mass Analysis (LAMMA) technique. The mass spectra are characteristic of both the hydrocarbon backbone of simple straight-chain polymers [polyethylene, poly(vinyl chloride), and poly(tetrafluoroethylene)] and of slight changes in side chain functionality [poly (phenyl methacrylate) and poly (benzyl methacrylate)]. The spectra show ion clusters having masses up to and beyond the monomer unit. This study indicates the power of the LAMMA technique for organic polymer materials analysis. Preliminary analysis of the mass patterns is given for the most probable positive and negative molecular cluster ions formed.