Nuclear magnetic resonance (NMR) parameters of 11B in borates and borosilicates, unlike those of many other nuclei such as 29Si and 27Al, vary only over limited ranges and have been thought to be insensitive to local structural environments. High-resolution NMR spectroscopy at high (14 T) and ultrahigh (21 T) fields yield precise 11B and 23Na NMR parameters for ulexite, which contains the pentaborate polyanion ([B5O6(OH)6]3−) as the fundamental building block (FBB). These NMR parameters are compared with ab initio theoretical calculations as implemented in WIEN2K, including optimization of the ulexite structure, determination of the electric field gradients (EFG) and consequently the nuclear quadrupole interaction (QI) parameters at the five distinct B sites, and calculations of the density of states (DOS). These calculations show that the magnitudes and signs of the EFG for [3]B and [4]B are determined by multiple factors, including the electron distributions in the B 2pz orbitals and their interactions with Ca-3p/O-2s orbitals. Most importantly, the calculated B 2pz orbitals at all B sites in ulexite are predominantly affected by the atoms within the fundamental building block, resulting in the insensitivity of the 11B QI parameters to the weak interunit interactions among FBB. Calculations with the water molecules removed from the ulexite structure provide further support for the strong intraunit interactions in FBB as a cause for the poor sensitivity of 11B NMR parameters to local structural environments, including hydrogen bonding, in borates.