Perovskite photovoltaics has witnessed an unprecedented increase in power conversion efficiency over the last decade. The choice of transport layers, through which photo-generated electrons and holes are transported to electrodes, is a crucial factor for further improving both the device performance and stability. In this perspective, we critically examine the application of optical spectroscopy to characterize the quality of the transport layer-perovskite interface. We highlight the power of complementary studies that use both continuous wave and time-resolved photoluminescence to understand non-radiative losses and additional transient spectroscopies for characterizing the potential for loss-less carrier extraction at the solar cell interfaces. Based on this discussion, we make recommendations on how to extrapolate results from optical measurements to assess the quality of a transport layer and its impact on solar cell efficiency.