Digital transformation has put tremendous pressure on employees to innovate with the use of information technology (IT). This paper explores the extent to which digital literacy and personal innovativeness contribute to individual’s innovative work behavior (IWB). To test our hypotheses, we apply double bootstrapping chained mediation analyses paired with relative importance analysis on a dataset collected from employees (N = 167) in a pharmaceutical company. The results showed the existence of a double-mediation chain whereby digital practices and attitude toward digitalized innovation mediate the positive relationship between digital literacy and IWB. Surprisingly, said chain was not supported for personally innovative individuals, indicating that digital literacy plays a relatively more important role in stimulating attitudes toward digitalized innovation and IWB. Our findings add further specificity to research on digital natives and may help organizations understand the role of digital literacy and personal innovativeness in organizationally-relevant outcomes, such as IWB.