Multi-field inflation models and non-Bunch-Davies vacuum initial conditions both predict sizeable non-Gaussian primordial perturbations and consequently anisotropic 𝜇-type spectral distortions of the cosmic microwave background (CMB) blackbody. While CMB anisotropies allow us to probe primordial non-Gaussianity at wavenumbers 𝑘 0.05 Mpc −1 , 𝜇-distortion anisotropies are related to non-Gaussianity of primordial perturbation modes with much larger wavenumbers, 𝑘 740 Mpc −1 . Through cross-correlations between CMB anisotropies and 𝜇-distortion anisotropies, one can therefore shed light on the aforementioned inflation models. We investigate the ability of a future CMB satellite imager like LiteBIRD to measure 𝜇𝑇 and 𝜇𝐸 cross-power spectra between anisotropic 𝜇-distortions and CMB temperature and 𝐸-mode polarization anisotropies in the presence of foregrounds, and derive LiteBIRD forecasts on 𝑓 𝜇 NL (𝑘 740 Mpc −1 ). We show that 𝜇𝐸 cross-correlations with CMB polarization provide more constraining power on 𝑓 𝜇 NL than 𝜇𝑇 cross-correlations in the presence of foregrounds, and the joint combination of 𝜇𝑇 and 𝜇𝐸 observables add further leverage to the detection of small-scale primordial non-Gaussianity. For multi-field inflation, we find that LiteBIRD would allow to detect 𝑓 𝜇 NL = 4500 at 5𝜎 significance after foreground removal, and achieve a minimum error of about 𝜎( 𝑓 𝜇 NL = 0) 800 at 68% CL by combining CMB temperature and polarization. Due to the huge dynamic range of wavenumbers between CMB and 𝜇-distortion anisotropies, such large 𝑓 𝜇 NL values at 𝑘 740 Mpc −1 would still be consistent with CMB constraints 𝑓 NL 5 at 𝑘 0.05 Mpc −1 in the case of very mild scale-dependence of primordial non-Gaussianity. Anisotropic spectral distortions thus provide a new path, complementary to CMB 𝐵-modes, to probe inflation with LiteBIRD.