Simply check the .az
attribute of the star once your observer object has determined the moment of rising or setting. For example:
import ephem
s = ephem.star('Sirius')
boston = ephem.Observer()
boston.lat = '42.37'
boston.lon = '-71.03'
boston.next_rising(s)
print s.alt, s.az
boston.next_setting(s)
print s.alt, s.az
Running this script at this moment gives me the encouraging output:
0:00:00.0 112:23:25.2
0:00:00.0 247:36:34.9
As you can see, the rising and setting routines have already established the moment of zero altitude, leaving the azimuth for you to read off and use!