An ultrafast route to prepare up-converting single β-phase NaYF:Yb,Ln (Ln: Er, Tm, or Tb) short nanorods (UCNRs) of high quality was developed. This new procedure affords reactive-surface nanorods that are easily coated by direct injection of suitable capping ligands. Thus highly crystalline nanorods with excellent UC fluorescence and good solvent-selective dispersion are obtained, which represents a significant advance in the field and enlarges their use for biomedical and other technological applications. Unlike other methodologies, the short reaction time provides a kinetic control over crystallization processes, and the β-phase and rod morphology is preserved regardless of the optically active Ln ion. The UC emission was finely tuned by using the most popular Yb/Tm and Yb/Er pairs. More importantly, UCNRs doped with the unusual Yb/Tb pair, with no ladder-like energy levels, provided a nice emission upon near-infrared excitation, which constitutes the first example of phonon-assisted cooperative sensitization to date in pure β-NaYF nanocrystals.