Background: Drug regimens for the treatment of drug-resistant tuberculosis (DR-TB) are composed of salvage drugs to which a patient has never been exposed to previously. Methods: A retrospective observational study was conducted in a DR-TB Center attached to a medical college in a metropolitan city using the database of category V patients (n = 100) who were prediagnosed and referred. The clinical records of the patients were reviewed for demographic data, history, sputum examinations, co-morbidities, and adverse drug reactions (ADRs). The therapy outcomes were assessed as per Revised National Tuberculosis Control Programme (RNTCP) guidelines. Results: Their mean age was 29.1 years; there were 57 males. Mean body weight was 41.8 kg. Pediatric patients (age 12–17) constituted 13%. All the patients had pulmonary TB. Of the 100 cases, 80 were Category IV failure; 5% were defaulters of Category IV; and 15% were treated with second-line drugs adequately in private. Durg-susceptibility test (DST) showed extensively drug-resistant TB (XDR-TB) in 63 and pre-XDR-TB in 37 patients. The outcomes of Category V treatment were cure (7%), died (33%), failed on therapy (4%), transferred out (16%), lost to follow-up (2%), and still on the therapy (35%). Various comorbidities were present in 25% patients. ADRs were seen in 44%, and peripheral neuropathy (18%) was the most commonly observed ADR. Conclusions: DR-TB patients were younger and males were more affected. Mortality of Category V regimen was high (33%). Most common comorbidities were anemia and hypothyroidism. Adverse reactions were common (44%); ADR peripheral neuropathy being the most common.