We sought to examine predictors of psychological distress among employees as well as the level of awareness and usage of available mental health resources by employees through their own organizations. The Malaysian Healthiest Workplace survey cross-sectional dataset was used to explore the association between psychological distress, a range of health conditions, as well as mental health resource awareness and usage in a sample of 11,356 working Malaysian adults. A multivariate logistic regression was conducted to determine predictors of high psychological distress. Comorbid illnesses that were associated with psychological distress were mental illness (OR 6.7, 95% CI 4.39–10.14, p = 0.001), heart conditions (OR 2.17, 95% CI 1.18–3.99, p = 0.012), migraines (OR 1.59, 95% CI 1.33–1.90, p = 0.001), bronchial asthma (OR 1.43, 95% CI 1.11–1.85, p = 0.006), and hypertension (OR 1.42, 95% CI 1.07–1.88, p = 0.016) compared to individuals with no comorbid conditions. A total of 14 out of 17 comorbid medical illnesses were associated with elevated levels of psychological distress among employees. Awareness and usage of support services and resources for mental health were associated with lower psychological distress. These findings extend the literature by providing further evidence on the link between chronic illness, occupational type, as well as awareness and use of mental health resources by psychological distress status.