Updated working method
My minSdkversion is 21, so I'm using ContextCompat.checkSelfPermission() method to grant permissions apart from also adding the <uses-permission android:name="android.permission.READ_EXTERNAL_STORAGE"/> in manifest. Thus, to get rid of the NullPointerException in spite of having files in your targeted directory, grant permissions as follows:-
MainActivity.java
public class MainActivity extends AppCompatActivity {
    /*Other variables & constants here*/  
    private final int READ_EXTERNAL_STORAGE=100;
    @Override
    protected void onCreate(Bundle savedInstanceState) {
        super.onCreate(savedInstanceState);
        setContentView(R.layout.activity_main);
        // ignore the button code
        Button btn = (Button) findViewById(R.id.button);
        btn.setOnClickListener(new View.OnClickListener() {
            @Override
            public void onClick(View v) {
                openWebView();
            }
        });
    
         /*---------------------------- GRANT PERMISSIONS START-------------------------*/
        // Main part to grant permission. Handle other cases of permission denied
       //   yourself.
        if(ContextCompat.checkSelfPermission(this, Manifest.permission.READ_EXTERNAL_STORAGE) != PackageManager.PERMISSION_GRANTED)
            ActivityCompat.requestPermissions(this,new String[] {Manifest.permission.READ_EXTERNAL_STORAGE},READ_EXTERNAL_STORAGE);
         /*---------------------------- GRANT PERMISSIONS OVER-------------------------*/
   }
And the function that list all the files (in MainActivity.java), thanks to 
@Yury:-
public void getDownloadedFile() {
        String path = Environment.getExternalStorageDirectory().toString()+"/Download/";
        Log.d("Files", "Path: " + path);
        File directory = new File(path);
        File[] files = directory.listFiles();
        if(directory.canRead() && files!=null) {
            Log.d("Files", "Size: " + files.length);
            for(File file: files)
                Log.d("FILE",file.getName());
        }
        else
            Log.d("Null?", "it is null");
    }