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Connections between metals and heterogeneous solid state materials form buried interfaces. These ubiquitous structures play an essential role in determining the performances of many nano- and microdevices. However, the information about the chemistry, structure, and properties of these real interfaces is intrinsically difficult to extract by traditional techniques. Therefore, approaches to efficiently discovering metalized interfaces are in high demand. Here, we demonstrate the transformation of nanoscale metal/oxide interface problems into surface problems through a novel metal-hydrogenation detaching method. We applied this technique to study the thickness dependence in Pb(Zr,Ti)O3 (PZT) ferroelectric thin films, a long-standing interface problem in a model metal/insulator device, and this allowed comprehensive surface analytical techniques to be adapted. A nonstoichiometric interfacial layer of 4.1 nm thick with low mass density, low permittivity, and weak ferroelectricity was quantified at the Pt/PZT interface and attributed to the preferential diffusions among the compositional elements. Targeted interface engineering by Pb rebalance led to a substantial recovery of ferroelectric properties. Our results therefore pave the way to a better understanding of metallized interface in ferroelectric and dielectric nanodevices. We hope that more useful information about metalized interfaces of other solid materials could, analogously, be accessed by surface analytical techniques.