I found a faster way to solve the problem, at least on realistically large datasets using:
df.set_index(KEY).to_dict()[VALUE]

Proof on 50,000 rows:

df = pd.DataFrame(np.random.randint(32, 120, 100000).reshape(50000,2),columns=list('AB'))
df['A'] = df['A'].apply(chr)

%timeit dict(zip(df.A,df.B))
%timeit pd.Series(df.A.values,index=df.B).to_dict()
%timeit df.set_index('A').to_dict()['B']

Output:

100 loops, best of 3: 7.04 ms per loop  # WouterOvermeire
100 loops, best of 3: 9.83 ms per loop  # Jeff
100 loops, best of 3: 4.28 ms per loop  # Kikohs (me)

In Python 3.6 the fastest way is still the WouterOvermeire one. Kikohs’ proposal is slower than the other two options.

import timeit

setup = '''
import pandas as pd
import numpy as np
df = pd.DataFrame(np.random.randint(32, 120, 100000).reshape(50000,2),columns=list('AB'))
df['A'] = df['A'].apply(chr)
'''

timeit.Timer('dict(zip(df.A,df.B))', setup=setup).repeat(7,500)
timeit.Timer('pd.Series(df.A.values,index=df.B).to_dict()', setup=setup).repeat(7,500)
timeit.Timer('df.set_index("A").to_dict()["B"]', setup=setup).repeat(7,500)

Results:

1.1214002349999777 s  # WouterOvermeire
1.1922008498571748 s  # Jeff
1.7034366211428602 s  # Kikohs

TL;DR

>>> import pandas as pd
>>> df = pd.DataFrame({'Position':[1,2,3,4,5], 'Letter':['a', 'b', 'c', 'd', 'e']})
>>> dict(sorted(df.values.tolist())) # Sort of sorted... 
{'a': 1, 'b': 2, 'c': 3, 'd': 4, 'e': 5}
>>> from collections import OrderedDict
>>> OrderedDict(df.values.tolist())
OrderedDict([('a', 1), ('b', 2), ('c', 3), ('d', 4), ('e', 5)])

In Long

Explaining solution: dict(sorted(df.values.tolist()))

Given:

df = pd.DataFrame({'Position':[1,2,3,4,5], 'Letter':['a', 'b', 'c', 'd', 'e']})

[out]:

 Letter Position
0   a   1
1   b   2
2   c   3
3   d   4
4   e   5

Try:

# Get the values out to a 2-D numpy array, 
df.values

[out]:

array([['a', 1],
       ['b', 2],
       ['c', 3],
       ['d', 4],
       ['e', 5]], dtype=object)

Then optionally:

# Dump it into a list so that you can sort it using `sorted()`
sorted(df.values.tolist()) # Sort by key

Or:

# Sort by value:
from operator import itemgetter
sorted(df.values.tolist(), key=itemgetter(1))

[out]:

[['a', 1], ['b', 2], ['c', 3], ['d', 4], ['e', 5]]

Lastly, cast the list of list of 2 elements into a dict.

dict(sorted(df.values.tolist())) 

[out]:

{'a': 1, 'b': 2, 'c': 3, 'd': 4, 'e': 5}

---

Related

Answering @sbradbio comment:

If there are multiple values for a specific key and you would like to keep all of them, it’s the not the most efficient but the most intuitive way is:

from collections import defaultdict
import pandas as pd

multivalue_dict = defaultdict(list)

df = pd.DataFrame({'Position':[1,2,4,4,4], 'Letter':['a', 'b', 'd', 'e', 'f']})

for idx,row in df.iterrows():
    multivalue_dict[row['Position']].append(row['Letter'])

[out]:

>>> print(multivalue_dict)
defaultdict(list, {1: ['a'], 2: ['b'], 4: ['d', 'e', 'f']})

Here are two other ways tested with the following df.

df = pd.DataFrame(np.random.randint(0,10,10000).reshape(5000,2),columns=list('AB'))

using to_records()

dict(df.to_records(index=False))

using MultiIndex.from_frame()

dict(pd.MultiIndex.from_frame(df))

Time of each.

24.6 ms ± 847 µs per loop (mean ± std. dev. of 7 runs, 10 loops each)
1.86 ms ± 11.6 µs per loop (mean ± std. dev. of 7 runs, 1000 loops each)

dict (zip(data['position'], data['letter']))

this will give you:

{1: 'a', 2: 'b', 3: 'c', 4: 'd', 5: 'e'}

I like the Wouter method, however the behaviour with duplicate values might not be what is expected and this scenario is not discussed one way or the other by the OP unfortunately. Wouter, will always choose the last value for each key encountered. So in other words, it will keep overwriting the value for each key.

The expected behavior in my mind would be more like Create a dict using two columns from dataframe with duplicates in one column where a list is kept for each key.

So for the case of keeping duplicates, let me submit df.groupby('Position')['Letter'].apply(list).to_dict() (Or perhaps even a set instead of a list)

One more simple way to convert the dataframe columns into dictionary

Dataframe:

  Position  Letter
0     1       a
1     2       b
2     3       c
3     4       d
4     5       e

Using dictionary comprehension

{k : v for k,v in df.values}

you get:

{1: 'a', 2: 'b', 3: 'c', 4: 'd', 5: 'e'}