[Jeffers24]

What am I doing wrong??

Only the first substitution is working in my advancesaettins entry, if I delete the first entry so the second entry becomes the first, then that entry works only that one works:-

<pathsubstitution>
  <substitute>
    <from>/storage/sdcard1/.Kodi SDCard/Pictures/Oldies/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\Oldies</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/201204 Apartment Oasis de la Cala/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\201204 Apartment Oasis de la Cala</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/201307 Spain with Kids/</from>
<to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\201307 Spain with Kids</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/201605 Caminito/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\201605 Caminito</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/201511 Karen/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\201511 Karen</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/200311 Ken's 60th and Retirement Do/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\200311 Ken's 60th and Retirement Do</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/200811 Ken's 65th Birthday/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\200811 Ken's 65th Birthday</to>
<from>/storage/sdcard1/.Kodi SDCard/Pictures/Yvette and Ken Miscellaneous/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Pictures\Yvette and Ken Miscellaneous</to>
<from>/storage/sdcard1/.Kodi SDCard/CDs/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\CDs</to>
<from>/storage/sdcard1/.Kodi SDCard/MP3 DLs/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\MP3 DLs</to>
<from>/storage/sdcard1/.Kodi SDCard/Video Singles/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Video Singles</to>
<from>/storage/sdcard1/.Kodi SDCard/Video Concerts/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\Video Concerts</to>
<from>/storage/sdcard1/.Kodi SDCard/TV Shows/</from>
    <to>C:\My Folders\Kodi\.Kodi SDCard\TV Shows</to>
  </substitute>
  </pathsubstitution>

Not sure without a debug log but you're doing way too much there - no need to pathsub each folder, just the root folders. So it looks as though all you really need is:

<pathsubstitution>
<substitute>
<from>/storage/sdcard1/</from>
<to>C:\My Folders\Kodi\</to>
</substitute>
</pathsubstitution>

Thanks that did the trick.

Is it possible to have more than one path substitution?

If yes would I include the 'from' and 'to' additional lines between the same 'substitute' lines?

[trogggy]

Is it possible to have more than one path substitution?

If yes would I include the 'from' and 'to' additional lines between the same 'substitute' lines?

Sure. I have about 15 by design (so I can use the same sources and library everywhere, absolutely not as advertised).
And I've just realised what your problem was:
The format is:

<pathsubstitution>
<substitute>
<from>xxx</from>
<to>yyy</to>
</substitute>
<substitute>
<from>zzz</from>
<to>aaa</to>
</substitute>
<substitute>
<from>bbb</from>
<to>ccc</to>
</substitute>
<substitute>
<from>ddd</from>
<to>eee</to>
</substitute>
</pathsubstitution>

I knew it didn't look right but not what was missing.