NaBiF4:Yb3+(20 mol%),Er3+(2mol%) phosphors (NBF:Yb,Er) were synthesized by a simple precipitation method. Several NBF:Yb,Er samples were made with different Na/F ratios (from 2/16 to 6/16 and 6/24). XRD and SEM measurements indicated that all the NBF:Yb,Er phosphors presented an hexagonal phase and morphology of microbars with sizes of 1–2 μm, respectively. According to the photoluminescence measurements, these phosphors emitted red/green emission bands at 541/655 nm and their emission intensity increased ⁓10.5 and 21 times for the green and red bands, respectively, after increasing the Na/F ratio from 2/16 to 4/16. In addition, the emission color was tuned from deep-green to yellow. Moreover, the Na/F ratio was decreased from 6/16 to 6/24, this in turn, changed the color emission from deep-green to orange. This last change of color occurred because the red emission was mainly favored by the following two cross relaxation (CR) processes CR1: 4I11/2 (Er3+)+ 4F7/2 (Er3+)→4F9/2 (Er3+)+ 4F9/2 (Er3+) and CR2: 4S3/2 (Er3+)+ 2F7/2 (Yb3+)→4I13/2 (Er3+)+ 2F5/2 (Yb3+). The second CR2 process also promoted the NIR emission at 1527 nm. Additionally, the lifetimes for the green and red bands increased from 393 to 420 μs and from 428 to 518 μs with the Na/F ratio, respectively. Thus, we presented here a new strategy to enhance the photoluminescence intensity and to control the emission-color/lifetimes without using extra co-dopants (as previously reported in literature).