A series of 6-(substituted-amino)-4H-s-triazolo[4,3-a][1,4]benzodiazepines was prepared for pharmacological evaluation, and, because of an interesting chemical isomerization, a similar series of 4-(substituted-amino)-6H-s-triazolo[4,3-alpha][1,4]benzodiazepines was also obtained. Pharmacological evaluation of these compounds demonstrated that8-choloro-1-methyl-6-piperidino-4H-s-triazolo[4,3-a][1,4]benzodiazpin e (10) had interesting activity in tests useful for detecting antianxiety activity, while the corresponding 4-piperidino derivative (15) had little activity in these tests. A brief discussion of a possible mechanism for the isomerization is also included.