Both cellulose nanofibrils (CNFs) and polydopamine (PDA) have attracted much attention due to their unique physical‐chemical properties and environmental benign nature. In this work, CNFs produced by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) ‐mediated oxidation (named as TOCNFs) were combined with PDA to prepare a novel pH/near‐infrared‐responsive (NIR) PDA/TOCNFs composite film, which was used for drug delivery. Tetracycline hydrochloride (TH) was used as a model drug. Results indicated that the TH loaded in the PDA/TOCNFs composite films could be released in an on‐demand fashion under NIR exposure or at lower pH conditions, and the mechanism of drug release was mainly driven by Case‐II transport. The prepared PDA/TOCNFs composite film can be a promising new drug delivery vehicle for the sustained drug release applications, attributing to their long time period drug releasing property, sensitive pH/NIR responses, as well as their biodegradability and biocompatibility.