Various lines of evidence suggest that memory for the relations among arbitrarily paired items acquired prior to testing can influence early processing of a probe stimulus. The event-related potential experiment reported here was designed to explore how early in time memory for a previously established face-scene relationship begins to influence processing of faces, under sequential presentation conditions in which a preview of the scene can promote expectancies about the to-be-presented face. Prior to the current work, the earliest component documented to be sensitive to memory for the relations among arbitrarily paired items was the late positive complex (LPC), but here relational memory effects were evident as early as 270–350 msec after face onset. The latency of these relational memory effects suggests that they may be the precursor to similar effects observed in eye movement behavior. As expected, LPC amplitude was also affected by memory for face-scene relationships, and N400 amplitude reflected some combination of memory for items and memory for the relations among items.