Is thin layer chromatography suitable to characterize distillate samples? Would I be correct if I state: Thin layer chromatography (TLC) is a separation method for non-volatile mixtures. Because distillate samples are pure, this would not be appropriate. 

I'm unsure and would like some insight into this.
Your statement is unnecessarily complicated and not easy to follow. You can use TLC as a quick way to assess the purity of a sample. It doesn't matter if your sample is a distillate or not. It only has to be non volatile as you said and soluble in some solvent or a mixture of solvents that can (the solvent/s) make it move on the TLC plate. 

I assume you want to use distillation to separate a mixture and TLC in order to assess the purity of your fractions. Obviously TLC becomes an unsuitable method for low b.p. distillates