We present UV broadband photometry and optical emission-line measurements for a sample of 32 Brightest Cluster Galaxies (BCGs) in clusters of the Representative XMM-Newton Cluster Structure Survey (REXCESS) with z = 0.06-0.18. The REXCESS clusters, chosen to study scaling relations in clusters of galaxies, have X-ray measurements of high quality. The trends of star formation and BCG colors with BCG and host properties can be investigated with this sample. The UV photometry comes from the XMM Optical Monitor, supplemented by existing archival GALEX photometry. We detected Halpha and forbidden line emission in 7 (22%) of these BCGs, in optical spectra. All of the emission-line BCGs occupy clusters classified as cool cores, for an emission-line incidence rate of 70% for BCGs in cool core clusters. Significant correlations between the Halpha equivalent widths, excess UV production in the BCG, and the presence of dense, X-ray bright intracluster gas with a short cooling time are seen, including the fact that all of the Halpha emitters inhabit systems with short central cooling times and high central ICM densities. Estimates of the star formation rates based on Halpha and UV excesses are consistent with each other in these 7 systems, ranging from 0.1-8 solar masses per year. The incidence of emission-line BCGs in the REXCESS sample is intermediate, somewhat lower than in other X-ray selected samples (-35%), and somewhat higher than but statistically consistent with optically selected, slightly lower redshift BCG samples (-10-15%). The UV-optical colors (UVW1-R-4.7pm0.3) of REXCESS BCGs without strong optical emission lines are consistent with those predicted from templates and observations of ellipticals dominated by old stellar populations. We see no trend in UV-optical colors with optical luminosity, R-K color, X-ray temperature, redshift, or offset between X-ray centroid and X-ray peak (<w>).