The EC2 instance report will include all costs associated to an instance while a reservation only covers compute costs. In other words, the EC2 Instance report will show and classify transfer costs associated to instances as "On-Demand" even if they are fully covered by RIs. The total "On-Demand" cost will be the sum of all compute and transfer costs for usage not covered by an RI along with the transfer costs associated to RI covered assets.
An easy way to compare the two charges is to pull in "Transfer Cost ($)" into the report via the Y-Axis dropdown and categorize by reservation type. The "Transfer Cost ($)" tab at the bottom will provide specifically the charges attributed to transfer costs.