Three commercially available dental silane primers, two single-phase prehydrolyzed and one two-component system were investigated for their composition, extent of hydrolysis, surface interactions, bond strength and interfacial topography when used on three representative porcelain alloys (AuPd, high-Pd, NiCr). Five tests, 1H FT-NMR, FTIR, GPC, ESCA and EPMA, were used to determine the composition and the surface interaction profiles. Shear tests were performed to assess the bond strength values. According to the results, all the primers contain γ-methacryloxypropyltrimethoxysilane (γ-MPTS) at concentrations 1.15–18.86 g/100 mL, two in ethanol and one in isopropanol. Traces of acetic acid were found in the prehydrolyzed primers. All the primers demonstrated partial hydrolysis of the methoxy groups. Prehydrolyzed primers exhibited a higher rate of hydrolysis and better orientation of hydrolyzed methoxy groups towards the NiCr alloy surface. Due to the extent of surface oxidation, the NiCr alloy provided more bonding sites for silanols than the other two types of alloys. The NiCr alloy demonstrated the highest shear bond strength values on smooth surfaces regardless of the type of primer used. The results of the present study suggest that active prepolymerized primers may provide significant advantages over two-component systems in the repair of NiCr porcelain fractures involving removal of the metal oxide layer.