A multifunctional alkoxysilane precursor for the sol–gel imprinting was designed and synthesized.

Aminoglutethimide-imprints in bulk (Bu) and spherical format (Sp) were successfully manufactured.

Bu gels presented better binding properties and higher selectivity and capacity than Sp gels.

Sp gels presented better mass transfer features.

Neither Bu nor Sp exhibited features as good as their acrylic counterparts.