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I assume that you use Windows (please never omit important information from your questions); on different OSes the answer may differ.

When you open a file from a file manager (another assumption I made), it doesn't matter which application was used to create the file. What the file manager uses when deciding which application to launch is which application is associated with the given file type in the operating system. You may have used MS Word to create a DOCX; or you could have used LibreOffice for that; or WordPad could create it - doesn't matter. What matters is that the file name ends with ".docx", and in the registry, .docx is registered to be handled with application X.

So what matters is how has it happen that LibreOffice got associated with the file type you used. If you use DOCX (as I suggested), then it only can happen during LibreOffice installation: there's a step where you choose if you want to associate LibreOffice with Word formats or not (see step 1.6 here). If you used ODT, then - well, LibreOffice always associates itself with its own native file type. But when you have both LibreOffice and Word co-existing on the same system, you need to know that the problems with taking over other program's associations are granted: e.g., Word forces re-association to itself, not only of own file types, but even ODT, which isn't its own format.

I assume that you use Windows (please never omit important information from your questions); on different OSes the answer may differ.

When you open a file from a file manager (another assumption I made), it doesn't matter which application was used to create the file. What the file manager uses when deciding which application to launch is which application is associated with the given file type in the operating system. You may have used MS Word to create a DOCX; or you could have used LibreOffice for that; or WordPad could create it - doesn't matter. What matters is that the file name ends with ".docx", and in the registry, .docx is registered to be handled with application X.

So what matters is how has it happen that LibreOffice got associated with the file type you used. If you use DOCX (as I suggested), guessed), then it only can could happen during LibreOffice installation: there's a step where you choose if you want to associate LibreOffice with Word formats or not (see step 1.6 here). If you used ODT, then - well, LibreOffice always associates itself with its own native file type. But when you have both LibreOffice and Word co-existing on the same system, you need to know that the problems with taking over other program's associations are granted: e.g., Word forces re-association to itself, not only of own file types, but even ODT, which isn't its own format.

You may search the Web for infinite number of answers how to associate a program to a given file type.