Melts of Bi-BiCl3-KCl and Bi-BiCl3 mixtures have been rapidly quenched into the glassy state at cooling rates of similar to 10(6) K/s. In this way glasses with electronic properties intermediate between the ionic and metallic state have been obtained for the first time. At low Bi-additions the optical characteristics of these glasses are very similar to those of the corresponding melts. Measurements of the electronic conductivity of Bi-BiCl3 glasses indicate that the transition from nonmetallic to metallic. behavior occurs at high Bi-doping of x(Bi) > 0.6 whereby the concentration dependence of the conductivity in the glassy and liquid state within experimental errors is the same. Changes of the microscopic structure of these glasses have been determined by small-angle X-ray scattering (SAXS) and by extended X-ray absorption fine structure (EXAFS) experiments. In the nonmetallic salt-rich glasses the SAXS-results exhibit Guinier-type scattering behavior consistent with Bi-clusters of spherical radii between 10 and 13 Angstrom. In the nonmetal-metal transition region the SAXS data follow a power law behavior indicating a coagulation of Bi-clusters and a percolative structure. From the EXAFS results an intra-cluster Bi-Bi distance of 3.11 +/- 0.02 Angstrom is derived which remains constant for the Bi-x (BiCl3)(1-x) glasses studied (0.2 less than or equal to x less than or equal to 0.8).