Secondary ion mass spectrometry (SIMS) was used to identify concentration gradients of polyacrylate samples. Applying discriminant function analysis (DFA) on the SIMS spectra resulted in visualized separations between different sample concentrations. We identified and separated concentrations of polyacrylate blends; from the separation we can construct calibration curves. The visual identification was followed in depth of a poly(fluoro-acrylate) film covered by poly(iso-bornylmethacrylate), which served as model sample of a photo-induced phase separated device. The combination of SIMS and DFA offers new possibilities to study the phase separation processes. Furthermore, it can predict how the phase separation creates mesoscopic layered electro-optical devices.