A quantitative understanding of the electromagnetic response of materials is essential for the precise engineering of maximal, versatile, and controllable light–matter interactions. Material surfaces, in particular, are prominent platforms for enhancing electromagnetic interactions and for tailoring chemical processes. However, at the deep nanoscale, the electromagnetic response of electron systems is significantly impacted by quantum surface-response at material interfaces, which is challenging to probe using standard optical techniques. Here, we show how ultraconfined acoustic graphene plasmons in graphene–dielectric–metal structures can be used to probe the quantum surface-response functions of nearby metals, here encoded through the so-called Feibelman d-parameters. Based on our theoretical formalism, we introduce a concrete proposal for experimentally inferring the low-frequency quantum response of metals from quantum shifts of the acoustic graphene plasmons dispersion, and demonstrate that the high field confinement of acoustic graphene plasmons can resolve intrinsically quantum mechanical electronic length-scales with subnanometer resolution. Our findings reveal a promising scheme to probe the quantum response of metals, and further suggest the utilization of acoustic graphene plasmons as plasmon rulers with ångström-scale accuracy.