A method is disclosed for modifying a catalytic molecular sieve for shape-selective hydrocarbon conversions comprises: a) selectivating said catalytic molecular sieve by contacting with a silicon-containing selectivating agent; and b) calcining the selectivated catalytic molecular sieve at high temperature calcination conditions comprising temperatures greater than 700.degree. C., which conditions are sufficient to reduce acid activity as measured by alpha value and increase diffusion barrier of said catalytic molecular sieve as measured by the rate of 2,3-dimethylbutane uptake, as compared to the selectivated catalyst. Catalytic molecular sieves thus prepared, such as silica-bound ZSM-5, and their use in hydrocarbon conversion processes such as aromatics isomerization, e.g., xylene isomerization, ethylbenzene conversion and aromatics disproportionation, e.g., toluene disproportionation are also disclosed.