The authors evaluated the effects of multileaf collimator (MLC) leaf width (2.5 vs. 5 mm) on dosimetric parameters and delivery efficiencies of intensity-modulated radiation therapy (IMRT) and volumetric-modulated arc therapy (VMAT) for head and neck (H&N) cancers. The authors employed two types of mock phantoms: large-sized head and neck (LH&N) and small-sized C-shape (C-shape) phantoms. Step-and-shoot IMRT (S&S_IMRT) and VMAT treatment plans were designed with 2.5- and 5.0-mm MLC for both C-shape and LH&N phantoms. Their dosimetric characteristics were compared in terms of the conformity index (CI) and homogeneity index (HI) for the planning target volume (PTV), the dose to organs at risk (OARs), and the dose-spillage volume. To analyze the effects of the field and arc numbers, 9-field IMRT (9F-IMRT) and 13-field IMRT (13F-IMRT) plans were established for S&S_IMRT. For VMAT, single arc (VMAT1) and double arc (VMAT2) plans were established. For all plans, dosimetric verification was performed using the phantom to examine the relationship between dosimetric errors and the two leaf widths. Delivery efficiency of the two MLCs was compared in terms of beam delivery times, monitor units (MUs) per fraction, and the number of segments for each plan. 2.5-mm MLC showed better dosimetric characteristics in S&S_IMRT and VMAT for C-shape, providing better CI for PTV and lower spinal cord dose and high and intermediate dose-spillage volume as compared with the 5-mm MLC (p < 0.05). However, no significant dosimetric benefits were provided by the 2.5-mm MLC for LH&N (p > 0.05). Further, beam delivery efficiency was not observed to be significantly associated with leaf width for either C-shape or LH&N. However, MUs per fraction were significantly reduced for the 2.5-mm MLC for the LH&N. In dosimetric error analysis, absolute dose evaluations had errors of less than 3%, while the Gamma passing rate was greater than 95% according to the 3%/3 mm criteria. There were no significant differences in dosimetric error between the 2.5- and 5-mm MLCs. As compared with MLC of 5-mm leaf widths, MLC with finer leaf width (2.5-mm) can provide better dosimetric outcomes in IMRT for C-shape. However, the MLC leaf width may only have minor effects on dosimetric characteristics in IMRT for LH&N. The results of the present study will serve as a useful assessment standard when assigning or introducing equipment for the treatment of H&N cancers.