Antiparallel polynucleotide chains refer to the structural orientation of the two strands of DNA, where they run in opposite directions. Each strand has a directionality defined by the 5' and 3' ends, with one strand running from the 5' to the 3' end while the other runs from the 3' to the 5' end. This unique arrangement is crucial for DNA replication, as it allows enzymes to function correctly and ensures that complementary base pairing occurs efficiently.