The problem occurs since the upgrade from Sol 9 to Sol 10leaves old shared libraries in /etc/vx/slib.
This is set to the LD_LIBRARY_PATH in /lib/svc/method/vxvm-sysboot that is used by Solaris 10 SMF startup scripts.

# ldd -v /usr/sbin/vxconfigd
Look for shared libraries "not found". These will usually be related to older libnsl.so.1 or older libc.so.1.

The OS upgrade does not clean up the /etc/vx/slib. This can be populated with minimal library set enough to get vxconfigd started during boot..
# mv /etc/vx/slib /etc/vx/slib.old
# mkdir /etc/vx/slib
# cp/etc/vx/slib.old/libvxdiscovery.so  /etc/vx/slib/libvxdiscovery.so  
#cp /etc/vx/slib.old/libvxscsi.so  /etc/vx/slib/libvxscsi.so

If /usris on a separate partition or volume then ALL the libraries indicated by ldd of the vxconfigd binary need to be placed in /etc/vx/slib.
# cp/usr/lib//libdevinfo.so.1  /etc/vx/slib//libdevinfo.so.1
# cp/usr/lib/libc.so.1 /etc/vx/slib/libc.so.1

# ldd -v /usr/sbin/vxconfigd
There should be no "not found" shared libraries.

Reboot the system to ensure that the vxconfigd starts correctly.