We have studied the interfacial characteristics of Ga-rich liquid Ga-Bi alloys at various compositions and temperatures up to 300 degreesC by different electron spectroscopies under ultrahigh vacuum conditions. In particular, the thickness and thickness profiles of Bi-rich wetting and surface freezing films have been measured. It is found that at the surface freezing transition the Bi film thickness jumps from similar to5 Angstrom to macroscopic values of over 100 Angstrom. This distinct behavior is discussed in comparison with the results in Ga-Pb. In addition, we report first scanning tunneling microscopy observations of the surface structure of a solidified Ga0.989Bi0.011 alloy after passing a surface freezing transition. The topology at room temperature is characterized by extended, atomically flat Bi terraces covered by nanosized triangular two-dimensional Bi islands. (C) 2004 American Institute of Physics.