De jure segregation happens when an individual/group are forced to be segregated by law. An example of this would be in American society during the early 20th century. There were state laws that kept blacks and whites segregated in public facilities, such as schools.
De facto segregation happens when individual groups are segregated by "fact" or chance. In this case, there is NO law compelling the individuals to be segregated. This is the biggest difference between the two forms of segregation. In de facto segregation, individuals choose to live in an all white or all black community.