We present deep polarimetric observations at 154 MHz with the Murchison Widefield Array (MWA), covering 625 deg2 centered on α = 0hand δ = -27°. The sensitivity available in our deep observations allows an in-band, frequency-dependent analysis of polarized structure for the first time at long wavelengths. Our analysis suggests that the polarized structures are dominated by intrinsic emission but may also have a foreground Faraday screen component. At these wavelengths, the compactness of the MWA baseline distribution provides excellent snapshot sensitivity to large-scale structure. The observations are sensitive to diffuse polarized emission at ∼54′ resolution with a sensitivity of 5.9 mJy beam-1 and compact polarized sources at ∼2.′4 resolution with a sensitivity of 2.3 mJy beam-1 for a subset (400 deg2) of this field. The sensitivity allows the effect of ionospheric Faraday rotation to be spatially and temporally measured directly from the diffuse polarized background. Our observations reveal large-scale structures (∼1°-8° in extent) in linear polarization clearly detectable in ∼2 minute snapshots, which would remain undetectable by interferometers with minimum baseline lengths of >110 m at 154 MHz. The brightness temperature of these structures is on average 4 K in polarized intensity, peaking at 11 K. Rotation measure synthesis reveals that the structures have Faraday depths ranging from -2 to 10 rad m-2 with a large fraction peaking at approximately +1 rad m-2. We estimate a distance of 51 20 pc to the polarized emission based on measurements of the in-field pulsar J2330-2005. We detect four extragalactic linearly polarized point sources within the field in our compact source survey. Based on the known polarized source population at 1.4 GHz and non-detections at 154 MHz, we estimate an upper limit on the depolarization ratio of 0.08 from 1.4 GHz to 154 MHz.