A mixture of n-octane (nC-8) and 2,2,4-trimethylpentane (224-TMP) was cracked over an alumina-pillared montmorillonite (Al-PILC) acid catalyst as a means of characterising its pore structure and shape selectivity. The shape selectivity of the catalyst was quantified by a time dependent parameter analogous to the constraint index, called the selectivity ratio (SR), and defined as log(fraction of nC-8 remaining)/log(fraction of 224-TMP remaining). The SR was measured over Al-PILC, a 0.16 wt% Pt loaded Al-PILC, a Y zeolite, and an amorphous silica-alumina. The SR was greater over Al-PILC compared with Y-zeolite even though the pore openings of the Al-PILC were of similar or larger size than those in the Y-zeolite. Doping Al-PILC with Pt caused a large increase in the SR. As found with constraint index measurements, internal pore dimensions and reaction mechanisms appear to be the determinants of SR. However, SR is better capable of discriminating larger pore microporous materials.