Yes.
For a Catholic looking to leave a marriage there are two separate process.
They can apply to have the marriage annulled within the Catholic Church. This is a well established institutional process and it's not that uncommon. Each region will have it's own tribunal that handles this stuff. Lots are granted annulment but also lots aren't.
Legally, the person generally has two choices, at least in countries where divorce is legal - apply for annulment if it's applicable, or divorce.
So you typically get three final possibilities that are ok by the Catholic Church: a) one you get a church annulment, and a legal annulment. Probably the least common, there are actually more grounds for church than legal annulment. b) church annulment, legal divorce. This is probably the most common scenario. People who do this are free to marry in the Catholic Church again. Or c) Church does not grant an annulment, but there is a legal divorce, so while they are legally no longer entangled the person is not able to remarry in the Church. This isn't necessarily considered a lesser outcome from a religious POV, it's recognized that even if the marriage is valid from a religious POV, it may be necessary to protect the other spouse or children from being linked legally, for example, to a drug addict.