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We show theoretically and experimentally the relationship between a signal's degree of polarization (DOP), all-order polarization mode dispersion (PMD), and the optical spectrum (and hence the data modulation format and pulse width), and that these effects must be taken into account when using the DOP for differential group delay (DGD) monitoring. We explain the theory behind how all-order PMD affects a signal's DOP, and observe the pulse-width dependence for 10-, 20-, and 40-Gb/s return-to-zero (RZ) systems as the duty cycle changes. We then analyze and show (via simulation and experimentation) the effects of different data modulation formats (RZ, carrier-suppressed RZ, alternate-chirped RZ, and differential phase-shift keying) on the DOP in a DGD monitor. We conclude that the measurable DGD range and DOP sensitivity in DOP-based DGD monitors are dependent on a signal's pulse width and the data modulation format. We also show the theory behind the effects of first- and second-order PMD on the maximum and minimum DOP.