In subtropical blackberry (Rubus L. subgenus Rubus Watson) production, inadequate winter chill causes poor and erratic budbreak, whereas high temperatures and heavy rainfall deteriorate late-season fruit quality. We examined the effects of four defoliants [zinc sulfate (ZS), potassium thiosulfate (KTS), urea, and lime sulfur (LS)] on defoliation, budbreak, yield, and fruit quality of ‘Natchez’ blackberry grown under inadequate chilling conditions in two consecutive growing seasons. Plants were treated with defoliants at 187 kg·ha−1 via spray application (1870 L·ha−1) at the beginning of chill accumulation (late December). A nonionic surfactant (Agri-Dex) was added at 0.5% (v/v) to all treatments including the water control. Cumulative chilling hours (<7.2 °C) at the experiment site were 209 and 134 in the first and second growing seasons, respectively. Defoliation was only 40.2% to 55.5% in the control, but it was induced moderately by LS (69.7% to 84.7%) and severely by the other defoliants (81.7% to 94.7%). Budbreak was induced most rapidly by urea application, followed by LS, KTS, and ZS, advancing by 17 to 66 days compared with the control. Consequently, urea, KTS, LS, and ZS increased early season yield by 2.79, 2.55, 0.87, and 0.31 t·ha−1, respectively, compared with the control (0.12 t·ha−1). By contrast, the final percentage of budbreak and total-season yield did not show significant treatment effects. KTS caused cane dieback and increased bud mortality, resulting in the lowest total-season yield among the treatments. Importantly, defoliants had no negative impact on berry size and soluble solids concentration. These results suggest that urea, LS, and ZS are effective bud dormancy-breaking agents for blackberry and that they could be an important adaptation tool for subtropical blackberry production. Among the three defoliants, urea appears to be the ideal chemical option because of its consistent efficacy, favorable safety profile, and low application cost.