There are several apps in liberkey which are enabled to run the respective 64 bit or 32 bit native application as per the Operating System or environment.

Means:- If CPU-Z is run from Liberkey in 32 bit environment it will launch x32 app and if the environment is 64 bit it will launch x64 app automatically.

Some of the apps with this Combo feature are:

7-Zip
CCleaner
ClavierPlus
ClocX
CPUz
CrystalDiskInfo
CrystalDiskMark
CurrPorts
Defraggler
DesktopOK
Everything
FastExplorer
FreeFileSync
HWMonitor
InfraRecorder
MediaInfo
Media Player Classic HC
Netscan
Networx
PngOptimizer
QDir
RealTimeSYnc
Recuva
RegFromApp
SearchMyFiles
Speccy
SysExporter
Unlocker
USB Deview
VLC Player
---------------------
But some applications such as Money Manager Ex etc. are only 32 bit in LiberKey though it is available in 64 bit portable format at the developers site.

Can I do it simply by creating two sub-folders named as x32 and x64 and putting the respective files into those folders or the launcher has to be modified for doing so. Please Explain...

I will also provide some other app names which do have x32 & x64 versions but are not yet made as combo in LiberKey.

Yes we must modify the app package in order to manage the 32 and 64 bit version of the app.