This paper is the first in a series undertaking a comprehensive correlation analysis between optically selected and X-ray-selected cluster catalogues. Unlike most of the X-ray/optical cluster correlations to date, the present paper focuses on the non-matching objects in either waveband. We investigate how the differences observed between the optical and X-ray catalogues may stem from (1) a shortcoming of the detection algorithms; (2) dispersion in the X-ray/optical scaling relations; or (3) substantial intrinsic differences between the cluster populations probed in the X-ray and optical bands. The aim is to inventory and elucidate these effects in order to account for selection biases in the further determination of X-ray/optical cluster scaling relations. This state-of-the-art study involving two well-validated cluster catalogues has shown itself to be complex, and it points to a number of issues inherent to blind cross-matching, owing both to pipeline shortcomings and cluster peculiar properties. These can only been accounted for after a manual check. The combined X-ray and optical scaling relations will be presented in a subsequent article.