The wide range of applications and promising possibilities of stacked 2D materials highlight the importance of studying heterostructures. The works presented in this dissertation tell a comprehensive story about the heterostructure composed of graphene and hexagonal boron nitride (hBN). Through the use of established characterization techniques such as transport and scanning tunneling microscopy, we will explore phenomena in the graphene/hBN heterostructure from the bottom up in three vertical stages. Stage 1 is the bottommost part of the heterostructure and deals with the accumulation of charged defects in hBN induced by an exposure to high electric fields. Stage 2 focuses on the graphene/hBN interface and how these layered materials work together to enable the corralling of relativistic charge carriers. Finally, stage 3 probes the exposed surface of a double-layered graphene system which is decoupled from hBN while still benefiting from its structural support. The interplay between these materials yields high quality and atomically resolved tunneling spectroscopy results that suggest the emergence of correlated phenomena in naturally occurring double-layered graphene.