Novel pyrimidine nucleoside-3,5-dicyanopyridine hybrids(4) or pyridine attached acylureas(5) were selectively and efficiently prepared from the reaction of 2’-deoxyuridin-5-yl-methylene malononitrile(1),malononitrile(2) and thiophenol(3) or from an unexpected uracil ring-opening and pyridine ring-forming sequence via the reaction of 1 and 3.It is the first time such a sequence has ever been reported. Novel pyrimidine nucleoside-3,5-dicyanopyridine hybrids (4) or pyridine attached acylureas (5) were selectively and efficiently prepared from the reaction of 2’-deoxyuridin-5-yl- methylene malononitrile (1), malononitrile (2) and thiophenol (3) or from an unexpected uracil ring-opening and pyridine ring-forming sequence via the reaction of 1 and 3. It is the first time such a sequence has ever been reported.