An instrumentation, measurement and post-processing technique is presented to characterize transmitters by multiple input multiple output (MIMO) Volterra series. The MIMO Volterra series is decomposed as the sum of nonlinear single-variable self-kernels and a multi-variable cross-kernel. These kernels are identified by sample averages of the outputs using inputs of different sample periodicity. This technique is used to study the HW effects in a RF MIMO transmitter composed by input and output coupling filters (cross-talk) sandwiching a non-linear amplification stage. The proposed technique has shown to be useful in identifying the dominant effects in the transmitter structure and it can be used to design behavioral models and compensation techniques.