The 15N and 13C chemical shifts of 6‐(fluoro, chloro, bromo, and iodo)purine 2′‐deoxynucleoside derivatives in deuterated chloroform were measured. The 15N chemical shifts were determined by the 1H15N HMBC method, and complete 15N chemical‐shift assignments were made with the aid of density functional theory (DFT) calculations. Inclusion of solvation effects significantly improved the precision of the calculations of 15N chemical shifts. Halogen‐substitution effects on the 15N and 13C chemical shifts of purine rings are discussed in the context of DFT results. The experimental coupling constants for 19F interacting with 15N and 13C of the 6‐fluoropurine 2‐deoxynuleoside are compared with those from DFT calculations. Copyright © 2009 John Wiley & Sons, Ltd.