The central difference between RCM and PMO is the way in which failure modes are generated.

Illustration of how RCM and PMO produce the same
result.
RCM seeks to analyse every
reasonably likely failure mode on every piece of equipment within
the system being analysed.
PMO generates a list of failure modes from the current maintenance
program, an assessment of known failures and by hazard analysis of
technical documentation - primarily Process and Instrumentation
Diagrams (P&IDs)
The differences in the two approaches mean that PMO deals with
significantly less failure modes than RCM and arrives at the
failure modes in a far quicker time frame. PMO’s selective
coverage means that the maintenance program that results will be
the same regardless of whether PMO or RCM is used.
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