A method has been developed which utilizes the experimental results from pyrolysis-gas chromatography (Py-GC) integrated with that from a Monte Carlo simulation to characterize the microstructure of a copolymer chain. The bridge between Py-GC and the Monte Carlo simulation is the relative triad peak intensities as well as the "number-average sequence length" values. By appropriate adjustment of the copolymerization parameters such as relative reactivity ratio, the triad intensity profile from a Monte Carlo simulation can be successfully fit to the Py-GC experimental values of relative trimer intensities. If the triad intensity profile and the value of "number-average sequence length" are a unique parameter set for every copolymer chain microstructure, all copolymer microstructure information on the real polymer can be explored based on the chain created by the Monte Carlo simulation. The development of this method makes it possible to extend microstructure determination beyond the current instrumentation limit.