After a CCD image of the Galilean satellites of Jupiter is obtained by a long focal-length telescope, we can compare the theoretical positions of these satellites with their pixel positions so as to obtain the calibration parameters of the CCD field of view. In theory, the measurement of relative positions for two satellites would have good accuracy when their separation is small enough. 120 CCD images taken by 1-m telescope at Yunnan Observatory in February 2003 are used to perform the experimental test. After we improve the centroid algorithm for the satellites and adopt the former halo-removal techniques (Peng et al. 2003, Peng 2005), the results show that the positional measurement of two small-separation satellites has precision as good as 0.01-0.02 arcsec. This precision has comparability as that from rarely happening mutual events of Galilean satellites. Moreover, because of its much more opportunities, it is believed that this kind of observations together with mutual event observations can be better used for the research in their celestial mechanics of Galilean satellites.